Dual-use micro encapsulation composition for hydrocarbons and detoxification of highly hazardous chemicals and substances

ABSTRACT

A two-component, water based micro encapsulation composition and method for the cleanup of hydrocarbon spills or contaminates on various surfaces and media. The two-part formulation includes a first solution including water in a predetermined ratio of a water soluble alkaline silicate solution having at least one alkali metal and a predetermined ratio of at least one water soluble surfactant; and a second solution including water, a predetermined ratio of water soluble acid, a predetermined ratio of water dispersible polymer, a predetermined ratio of water soluble hydrotrope, and a predetermined ratio of at least one water soluble flocculating agent. A method of using the two-part formulation includes preparing the two-part formulation, allowing the first solution to contact the hydrocarbon or chemical contaminate; allowing the second solution to contact the first solution and contaminate to form a homogeneous mixture; and removing the homogeneous mixture.

This application claims the benefit of U.S. Provisional PatentApplication Ser. No. 61/022,153 filed on Jan. 18, 2008 and incorporatessaid provisional application by reference into this document as if fullyset out at this point.

FIELD OF THE INVENTION

The present invention relates, generally, to a composition and methodfor remediation of hydrocarbon spills. More particularly, the presentinvention relates to a two-component water based micro encapsulationcomposition and method for the cleanup of hydrocarbon spills orcontaminates on a number of different surfaces and media.

BACKGROUND OF THE INVENTION Micro Encapsulation

There are many sites contaminated with hazardous organic substances.These contaminants permeate and adsorb onto soils, diffuse tointerstitial saturated zones, dissolve into ground waters, and migrateto subsurface aquifers over time. Contaminants may strongly adsorb onsoil structures and be only slightly water soluble, making removaldifficult. Thus, the ease of contaminant transport within and removalfrom the soil by most commercially acceptable technologies is variableat any particular site. Likewise, contaminants may be resistant tonormal subsurface chemical and biological degradation processes, thuslimiting the selection of a treatment process.

Depending on the processes, soil, sludge or aggregate remediationtechnologies are often divided into three categories. One group useschemical reduction, oxidation, thermal destruction or biochemical meansto change the pollutants into non-hazardous products of differentchemical composition. Examples are catalytic dehalogenation, Fentonoxidations, ozone, thermal treatments such as incineration andanaerobic/aerobic bioremediation either in situ or ex situ, bioventing,bioslurry, biofiltration and anaerobic dechlorination.

A second category consists of mass transfer technologies that usephysical or chemical means to take the contaminants out of the soilfollowed by treatment or destruction in another process step. These areoften called “Pump and Treat” technologies. Steam stripping, soil vaporextraction, soil washing, low or high-temperature thermal desorption andsolvent extraction are examples of this second technology category.These technologies have many limitations. Most are not effective attreating all contaminants in the contaminant group. For example,halogenated compounds are less amenable to bioremediation thannon-halogenated compounds. Likewise, with the popular Soil VaporExtraction technology, the heavier, less volatile compounds are moredifficult to remove from subsurface soil. Many innovative treatmenttechnologies, far too numerous to discuss in detail, fall into thesefirst two categories; however, none are a panacea.

The third category of remediation technologies is comprised oftechnologies that bind contaminants into a solid matrix. Anycontaminants leached into the environment are reduced to levels belowthose regulated by governmental agencies. There are many innovations inthe stabilization and solidification technologies that macro encapsulatecontaminants or contaminated soil into a solid monolith afterprocessing. Nine distinct innovative processes or groups of processes inthis third category include: (1) bituminization, (2) emulsified asphalt,(3) modified sulfur cement, (4) polyethylene extrusion, (5)pozzolan/Portland cement, (6) radioactive waste solidification, (7)sludge stabilization, (8) soluble phosphates, and (9)vitrification/molten glass. The biggest problem with these technologiesis that they are limited to primarily inorganic more so than organiccontaminants. The technology of the present invention is similar tosolidification and stabilization except it is based on microencapsulation techniques and works very well with organic contaminants.

The prior art is abundant with references (U.S. Pat. No. 3,837,872, U.S.Pat. No. 4,518,508, U.S. Pat. No. 4,581,162, U.S. Pat. No. 4,600,514,U.S. Pat. No. 4,622,175, U.S. Pat. No. 4,909,849 among others) tomethods of treating wastes with sodium silicate and a pozzolanic settingagent such as Portland cement, fly ash, kiln dust, lime, gypsum orcalcium carbonate to react with each other in animmobilization/stabilization method forming a large chemically andmechanically stable macro encapsulated water insoluble solid. Some ofthe cement stabilization processes show good short-term results withmetals, but very few show good long-term stability, especially withorganics.

In other prior art, Heacock (U.S. Pat. No. 5,295,761) formulated sodiumsilicate with a glycol and sodium methyl silanolate. This compoundreferenced as sodium methyl silanolate, CH₃Si(OH)₂O⁻Na⁺, is better knownas sodium methylsiliconate available from Dow Corning and in othertechnologies is used as a hydrophobing agent. Sodium methylsiliconate iscommercially used with sodium silicate as a sealant for concrete.According to Heacock, as the soil is mechanically pulverized, air iscontinuously sparged into the soil as the formulation is applied.Heacock believes that the present formulation breaks down the chemicalcomposition of the hydrocarbon contaminants in soil to inhibit thevolatilization of any toxic components into the atmosphere. During theprocess, the pH of the soil is monitored and when it reaches a pH of 7,Heacock claims “hydrocarbon concentrations in the soil are effectivelyneutralized.” Actually, the inventor of the present application believesair sparging must provide great assistance in delivering the volatilecontaminants from the soil into the air to produce the results obtainedin the single example provided, because to one skilled in the art, forthis formulation to have any reactivity toward hydrocarbon decompositionis doubtful.

Other examples of dubious prior art are represented by Loomis (U.S. Pat.No. 5,478,389) and Spence (U.S. Pat. No. 6,436,884) whereby Spenceactually questions the validity of Loomis's patent, but both havesimilar compositions of a sodium silicate, a surfactant and a polyolsuch as ethylene glycol. Loomis mixes an aqueous formulation of the artin a jar with the various contaminants such as an insecticide, aromatichydrocarbons, and chlorinated hydrocarbons. As the jar sets for two tothree weeks, a two phase system results with the organic contaminantspartitioned into the solid silica precipitate formed in the bottom ofthe flask. The sample analyzed for contaminate was taken from the upperwater layer and contrasted with the control. Spence takes the art onestep further to claim extremely low levels of contaminant cleanup onsurfaces contaminated with poly chlorinated biphenyl (PCB) compounds anddismisses the ability of Loomis's invention to do the same. Furthermore,Spence claims his invention destroys PCB compounds in an alkali metalcatalyzed dechlorination reduction reaction in less than 12 hours.

Loomis's preferred formulation was reproduced in our laboratory only tofind two-phase incompatibility with the T-Mulz surfactant. Shaking thesample produced a hazy solution. When 3 ml of the formulated sodiumsilicate was mixed with 3 ml of used motor oil, a low level emulsionformed. Three ml of an 8 percent by weight (using 75% phosphoric acid)phosphoric acid solution was added to the mixture to form a microencapsulated oil. The resultant mass bled about 50 percent of the oilfrom the mass over a few days. The experiment was repeated using theacidic polymer formulation of the invention and a significantimprovement was obtained forming a wet oily pasty solid, although theimprovement is far inferior to the micro encapsulation samples obtainedwith the “dual use” silicate and polymer formulations of the invention.

In U.S. Pat. No. 5,076,938, Noonan et. al. proposed a two componentmethod for encapsulating hydrocarbon systems with the combination of anemulsifier solution and a sodium silicate solution. The method comprisesthe addition of an acidic emulsifier solution to a hydrocarbon, thenadding a sodium silicate solution to the emulsified hydrocarbon. Themixture changes to a thick agglomerated gel. According to the patent,the preferred emulsifier may consist of 30% concentrated phosphoricacid, 8% citric acid, 4% sodium chloride, 5% nonyl phenol ethoxylate, 6%sodium dodecyl benzene sulfonic acid, 4% linear alcohol ethoxylate, 3%phenyl glycol ether and 40% water. Sol gel systems formed byprecipitation of sodium silicate in this manner have been known foryears. They lack the cohesive ability to bind the contaminant into thesol gel through surfactants alone, compared to the inventiveformulations. Both the emulsifier and the silica solution of Noonan'sinvention are considered corrosive by US Department of Transportationstandards since the pH of the concentrates are less than 2 and greaterthan 12.5 respectively.

In 1997, the current inventor Burns (U.S. Pat. No. 5,678,238), showed itwas possible to formulate a sodium silicate system with an emulsifyingamount of selected surface active agents and utilize an acidicpolyacrylate to micro encapsulate the contaminant into a non-leachablesilicate mass. This prior art was suitable for use on hydrocarboncontaminants and selected chemicals for cleaning surfaces and bulkcontamination from spills. The polymer agent aids in binding thehydrocarbon in the micro encapsulated mass to reduce hydrocarbonsyneresis in the wet form.

The inventor's previous art (U.S. Pat. No. 5,678,238) taughtimprovements over Noonan, in that Noonan's prior art is incapable ofcleaning surfaces as a single component micro encapsulation systembecause the silica does not have emulsifying capacity. Also, Noonan'sacidic emulsifier lacks a suitable binding polymer in the acidicsolution that is responsible for the improved micro encapsulationproperties. U.S. Pat. No. 5,678,238 is superior to that of Heacock (U.S.Pat. No. 5,295,761) because Heacock does not incorporate surfactants inthe silica system for desorbing the hydrocarbon contaminants from thesoil. Moreover U.S. Pat. No. 5,295,761 relies on air injection to drythe silica in the soils whereby there is no control over air strippingof the volatile hydrocarbons that undoubtedly affects the results.Likewise, Loomis (U.S. Pat. No. 5,478,389) and Spence (U.S. Pat. No.6,436,884) do not have two component systems to micro encapsulate bulkcomponents and a single component system will not work for bulkcontamination. Neither Loomis nor Spence have the ability for rapidspill clean up being a single component system.

The current invention shows unexpected improvements over all of theprior art in its capacity to micro encapsulate hydrocarbons andchemicals down to low ppm levels of leachability at half theconcentration of the inventor's previous prior art and it can optionallybe formulated for “dual-use” with a third component for detoxificationof highly hazardous substances prior and during the micro encapsulationprocess.

CB Agent Detoxification

Terrorist threats involving weapons of mass destruction such as CBAgents have a worldwide presence. The use and the threat of CB Agent useis of paramount concern to the United States national defense as well asstate and local law enforcement. A CB Agent attack can be localized ordispersed to affect a large population.

Certain chemical warfare agents share chemical and physicalcharacteristics that present an opportunity for countermeasuredevelopment. The CW G-Agents are examples of phosphorus containingcompounds. Mustard is a sulfur containing CW H-Agent. VX is an exampleof the group known as CW V-Agents with chemistry similar to that ofinsecticide families. In each of these cases, after these compounds haveundergone certain types of chemical reactivity, they loose much of theirtoxicity and are rendered harmless. However, because of the extremelevel of toxicity for these compounds, they require complete reaction ina very short time period.

Presently, the most common CB Agent decontamination procedures atforward operating locations involve spraying a liquid solution or foamon the exterior surface of the military asset. The military's currentdecontaminating solutions (Decontaminating Solution 2 (DS2), and supertropical bleach) are corrosive and (in the case of DS2) containaggressive organic solvents. While several alternative products areavailable that have reduced toxicity with lower risk of damage tomaterials, these products take significantly longer than currentdecontaminating solutions to destroy CB Agents.

Other methods (Tadros U.S. Pat. No. 6,566,574) have recently beendeveloped for CW Agent decontamination or detoxification. For exampleEasyDecon™ or MFD (also known as DF200) is a decontaminating foamformulation developed by Sandia National Laboratories and now availablefrom EnviroFoam Technologies, Inc. or MODEC Inc. While the product hasbeen demonstrated to be effective against a range of CB agents, itrequires a residence time of 15 minutes to one hour to destroy CBagents. For some agents, this is substantially longer than the residencetime required by the military's current decontaminating solution (DS2)and the present inventive application. The formulation also leaves aliquid residue from the surfactants and alcohols. Furthermore, aneffectiveness discrepancy has been reported by the EPA in the anthraxsimulant test results for decontaminating six logs of Bacillus subtillisspores on a hard nonporous surface at one hour contact time as reportedunder EPA Contract No. 68-C-02-067 “Compilation of Available Data onBuilding Decontamination Alternatives” EOA/600/R-05/036, March 2005.

QAC Decontaminant Solution, developed by the Navy Surface Warfare Center(NSWC) developed a decontaminating solution based on quaternary ammoniumcompounds and a solid form of hydrogen peroxide. From the prior art(Cronce U.S. Pat. No. 5,760,089 and U.S. Pat. No. 5,859,064), the bestdetoxification data is presented for the following Agents: VX: (37% in30 sec. and 95% in 60 min.), Mustard: (20% in 30 min. and 66% in 60min.) and GD: (99% in 30 sec. and 99+% in 60 min.). These results areinferior to those obtained with the present application. Furthermore,the preferred composition contains 20% of the benzyltrialkyl ammoniumchloride salts and 30% of isobutanolamine as a corrosioninhibitor-solvent. These materials would remain as a waste residue thatcould be construed as hazardous whereas any components of the inventiveformulations would be micro encapsulated.

The M100 Sorbent Decontamination System is another form ofdecontamination development by the US Army. This system could also beused on sensitive equipment. It consists of fabric mitts containingabsorbent particles that capture chemical agents. These suffer from thefollowing disadvantages 1) They are not effective against biologicalagents. 2) They are impractical for use on large surfaces of materials,parts or components. 3) They require personnel to come in close contactwith the agents. This increases their risk of exposure if theirprotective gear is damaged or defective. 4) Agents can slowly desorbfrom the material over time. Thus, the contaminated sorbents must behandled as hazardous materials and properly treated to eliminate thehazard.

The L-Gel foam products, developed by Lawrence Livermore combine acommercially available oxidizer (Oxone) with a colloidal amorphoussilica gelling agent (Cab-O-Sil EH-5 fumed silica) to create athixotropic gel that will adhere to walls and ceilings, and othermaterials like a paint. The mixture is spray applied and once dry, itcan be vacuumed up. Decontamination with L-Gel takes about 30 minutesafter application which is still to slow to be effective. It eventuallydries out in about six hours and can be removed by vacuuming.

CSI-1, available from Chemical Solutions International, is a productdesignated specifically to reduce the viability of anthrax. Testing ofCSI-1 with 10,000,000 spores indicates a reduction of viable spores to<500 after 30 minutes. After 2 hours, the result was a complete loss ofspore viability. According to the MSDS, it contains a ethylene glycolbutyl ether, aryl alkyl ammonium chloride, and glutaraledehye. It mustbe applied to the surface in sufficient quantities that it will stay wetfor 2 hours, then wipe clean with wet paper towels until clean. Thecurrent invention can take the viable anthrax simulant spores to acomplete loss of spore viability in less than two minutes.

Other technologies include the use of chlorine dioxide, TechXtract(Environmental Extraction Technologies, Inc.), CASCAD (Canadian AqueousSystem for Chemical—Biological Agent Decontamination), paraformaldehyde,and methyl bromide. Although each of these technologies each have theirown merits, none are a panacea.

SUMMARY OF THE INVENTION

The present invention relates to a two-component water based microencapsulation composition and method for the cleanup of routinehydrocarbon spills or contaminates on a number of different surfaces andmedia. Moreover, the present invention relates to an improved microencapsulation composition with ability to be promptly modified when theneed arises for the “dual-use” purpose of rapidly detoxifying highlyhazardous materials into significantly less hazardous by-products andthen micro encapsulating the less hazardous by-products from thedetoxification. Such detoxification component may be in the form of areactive entity such as an oxidation agent added to one of the two microencapsulation formulations just prior to detoxification. After a time,then the other micro encapsulation formulation is added to theby-product mixture containing the first micro encapsulation formulationcontaining any residual detoxifying component for the purposes ofcompleting the micro encapsulation. Such highly hazardous materialsinclude Toxic Industrial Chemicals (TICs), Toxic Materials (TMs) as wellas Chemical Biological Agents (CB Agents).

More particularly, the invention relates to two liquid chemicalformulations that can be used together to convert liquid organic wastesinto solid materials and significantly reduce the aqueous leachabilityof hydrocarbon and chemical spills on surfaces for removal or toremediate contaminated media. The addition of a third reactive componentto either the first or the second formulation can produce a modifiedformulation capable of rapidly oxidizing highly hazardous materials tosubstances of much lower toxicity. Within a few minutes, the secondformulation may be added for the purpose of micro encapsulating the lesshazardous by-products in a non-leachable solid form. Even moreparticularly, the inventive micro encapsulated solid may initially stillcontain very low ppm-ppb levels of unoxidized TICs, TMs or CB Agentsalong with the by-products, but because they are micro encapsulated, thetoxicity is further mitigated by reduced availability or vaporsuppression of the TICs, TMs or CB Agents in the microcapsules. Thesecond micro encapsulation component also brings the pH of the mixtureto neutral, thus hastening the decomposition of any residual oxidizingcomponent to non hazardous materials. TICs and CB Agents areself-explanatory in meaning, but TMs may include for example biologicalsubstances such as blood borne pathogens, certain infectious medicalwastes or nano size inorganic wastes materials such as asbestos that maybe encapsulated.

In one aspect, this invention is directed to demonstrate that thepreferred embodiments of the invention involve liquid chemicalformulations that may be applied by spraying or misting the contaminatedsurface or media and immediately form a solid micro encapsulate ordetoxify the highly hazardous substance with subsequent microencapsulation into a solid medium.

The present invention disclosed and claimed herein, in one aspectthereof, comprises a water based two-component micro encapsulationsystem with the ability to micro encapsulate hydrocarbons and chemicalsinto a solid non-leachable form. The first formulation of thetwo-component system is an aqueous, alkaline formulation withpredetermined ratios of an alkaline water soluble silicate solutionhaving at least one alkali metal and a predetermined ratio of watersoluble surface active agents for detergency, penetration andcontaminant emulsification. Depending on the choice of the formulationcomponents, a hydrotrope surfactant is sometimes necessary formaintaining the stability of the solution.

The second formulation of the two-component micro encapsulation systemis an aqueous acidic polymer formulation with a predetermined ratio ofan acid, an improved polymer flocculent-inorganic coagulant mixture forbinding the dispersed active agent in a silicate core matrix, aquaternary surfactant, and a hydrotrope for maintaining the stability ofthe micro encapsulate.

For micro encapsulation of hydrocarbons and chemicals, the firstalkaline formulation is applied to the contaminant followed byapplication of the second acidic polymer formulation. The pH of theresultant solid micro encapsulated material with a water-wet surface isneutral. The surface of the micro encapsulate contains only extremelylow levels, if any, of the hydrocarbon or chemical contaminant. As thewater evaporates the solid becomes a dry powder with the appearance oftalc and often, the color of the contaminant.

The present invention disclosed and claimed herein, in another aspectthereof as a “dual use” detoxifying and micro encapsulation system, maycontain an optional third detoxifying agent incorporated into the firstalkaline formulation (if the detoxification agent is alkalinecompatible) and added to the highly toxic contaminant for the purposesof first, rapidly detoxifying highly hazardous contaminant. After apredetermined detoxification time (usually a few minutes), then thesecond aqueous acidic polymer formulation is added to the mixture of thefirst alkaline formulation containing the detoxifying agent for thepurposes of completing the micro encapsulation process to form anon-leachable solid. The modes of detoxification include, but are not tobe limited to, alkaline nucleophilic hydrolysis, alkaline oxidation andacidic oxidation.

The present invention disclosed and claimed herein, in yet anotheraspect thereof as a “dual use” detoxifying and micro encapsulationsystem, may contain an optional third detoxifying agent incorporatedinto the first acidic polymer formulation (if the detoxification agentis acid compatible) and added to the highly toxic contaminant for thepurposes of first, rapidly detoxifying highly hazardous contaminant.After a predetermined detoxification time (usually a few minutes), thenthe second aqueous alkaline formulation is added to the mixture of thefirst acidic polymer formulation containing the detoxifying agent forthe purposes of completing the micro encapsulation process to form anon-leachable solid. The two-component micro encapsulation system hasunique distinguishing characteristics that make it versatile for manydifferent applications.

The present invention disclosed and claimed herein, in another aspectthereof as a “dual use” detoxifying and micro encapsulation system,provides a benefit of binding any very low level residual highlyhazardous contaminant on a molecular level in the micro encapsulatefurther reducing the level of toxicity in the environment. Furthermore,the significantly less hazardous by-products of reaction with thedetoxifying agent and the highly hazardous contaminant are likewisebound on a molecular level in the micro encapsulate allowing for a solidform of waste that may be collected for further treatment or disposalleaving no liquid by-products and no lasting environmental impact

The present invention disclosed and claimed herein, in another aspectthereof as a “dual use” detoxifying and micro encapsulation system,provides a further benefit of neutralizing any residual detoxifyingagent into a non-hazardous entity. Furthermore, of greatest benefit isthat detoxification in the “dual use” system is very rapid on the orderof a few minutes which is of utmost importance with the highly hazardoustendency of CB Agents.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT Biological WarfareAgents

Toxicants are defined as any chemical or biological compound or agentthat can cause death or permanent harm to humans or animals.Neutralization is defined as the mitigation, detoxification,denaturation or destruction of toxicants to the extent that thetoxicants no longer cause acute adverse effects to humans, animals orother life forms. There are hundreds of Biological Warfare Agents (BWAgents) available for use by terrorists. They are grouped into thecategories of spore forming bacterium (anthrax), vegetative bacterium(plague, cholera), virus (smallpox, yellow fever) and bacterial toxins(botulism, ricin). Spores are the most difficult microorganisms to kill.An example of a spore agent is Bacillus anthracis or anthrax. Spores aretough and environmentally durable, so they are prime agents of interestas offensive weapons. Bacillus subtilis var. niger (formerly Bacillusglobigii) is a common non-pathogenic soil bacterium. B. globigii is nolonger a recognized name, and at least some of these now are called B.subtilis (but not B. subtilis var. niger). B. subtilis var. niger is nolonger a recognized name, and at least some of these isolates are nowcalled Bacillus atrophaeus.

B. anthracis, which exists world-wide in nature (often in the soil), isa spore-forming organism, the spore being a hardy form that easily lendsitself to use as a warfare agent. The B. anthracis coat is of particularinterest because the spore is the infective particle for anthraxbacterial disease. Like a golf ball, anthrax spores are made of manylayers of material, which protect DNA in the core. (Journal ofBacteriology, Vol. 186, pp. 164-178, January 2004)

The spores causing anthrax are 1 to 1.5 micrometers in size, rod-shaped,odorless, and tasteless. Inhaling between 8000 and 50,000 spores (alethal amount, easily inhaled in one breath) can cause the disease'sonset. Fifty thousand spores in a glass dish are invisible to the nakedeye. To help comprehend how small the spores are, one common houseflycan carry about 7.35 billion spores attached to its external body hairs.Consequently, if 50,000 spores constitute a theoretically lethal dose, ahousefly could carry a lethal dose for over 100,000 individuals.

Vegetative cells are more common as agents, but they are less resilientin the environment making them more difficult to use in an offensivecapacity. Examples are plague or cholera and the simulant for vegetativecells is Erwinia herbicoli. Viruses require a host to replicate, and area rising threat because many are very survivable in the environment.Examples of a virus are smallpox or yellow fever and because specificsimulants do not exist for these viruses, a bio phage such asBacteriophage MS2 is typically used for testing. The fourth class ofbiological agents are toxins. Although less toxic than most organisms,the toxins are more easily produced in many cases and are verysurvivable. The most prominent toxins are botulism and ricin. A simulantfor biological toxins is ovalbumin. These simulant organisms are nottypically classified as human pathogens and are selected based on theirdocumented lack of toxicity to healthy humans.

The mechanism for the destruction of BW agents may not be as wellunderstood as that for Chemical Warfare Agents (CW Agents). In the caseof vegetative bacterial cells and viruses, the kill mechanism is mostlikely due to the oxidizing effect of oxidizers such as hydrogenperoxide. However, hydrogen peroxide concentrations from 10-20% arerequired for denaturation of anthrax spores, which are the moreresistant BW Agents. The spore DNA must be exposed to the oxidizer todetoxify the spore agent. The spore coat protects the DNA and must bebreached to effectively kill the spore agent. A possible mechanismconfirmed by Tadros U.S. Pat. No. 6,566,574 for spore kill is thatcationic surfactants can soften and disrupt the spore coat resulting inbreeches through which hydrogen peroxide can enter and attack the sporeDNA.

BW Agents—Anthrax Simulant Detoxification with U.S. Pat. No. 5,678,238

The commercial alkaline TERRACAP™ 3000 additive and acidic TERRACAP™4000 additive are the commercial products of the U.S. Pat. No. 5,678,238invention available from RTA Systems, Inc., Oklahoma City, Okla. Apreliminary test was conducted by a government official with theoriginal products from this art to determine if the existing TERRACAPformulations could micro encapsulate a anthrax simulant, Bacillusglobigii (Bacillis subtilis var. niger ATCC 9372). The result wasreported that the micro encapsulation agents had a 75% efficacy rate atdenaturing or micro encapsulation of the anthrax simulant. Whether theefficacy reduction was due to the micro encapsulation process oractually denaturing of the simulant or a combination of both was notreported. Although the original stand-alone result is far from havingutility, the result was encouraging and allowed the applicant to receiveAir Force SBIR and later OCAST funding for this work.

The research effort was aimed at substantial improvements andmodifications to the existing art to create utility as a “dual-use”system that can provide improved micro encapsulation of mundanehydrocarbons used in transportation and certain characteristic hazardouswastes that contaminate surfaces and media. The “dual-use” concept isinvoked when hazardous or highly hazardous chemicals or substances areencountered whereby the modified system with a detoxification agentincorporated can detoxify the hazardous or highly hazardous chemicals orsubstances just prior to or during the micro encapsulation process. Thenovel concept of a “dual-use” system and providing utility fromadditional protection by detoxification of the hazardous or highlyhazardous chemicals or substances with subsequent micro encapsulationprovides an extra level of protection to life and the environment.

The initial modification to the TERRACAP 3000 utilized an alkalinestable quaternary ammonium compound, cetylpyridinium chloride (CPC) andthe activator tetrasodium ethylenediaminetetraacetate, the combinationwhich is known to have sporicidal activity through out a pH range.Efforts were not made to optimize the concentration of the sporicidalagent except that the 1 to 1 ratio of Quat to activator (0.5 weightpercent each) provided by the manufacturer was followed. CPC isavailable as Sumquat 6060/CPC from Zeeland Chemical Inc., (ZeelandMich.). In these preliminary tests, the best spore kill levels were94.6% in two minutes and with no change (95.1%) at 60 minutes, animprovement over the original TERRACAP 3000 and TERRACAP 4000 microencapsulation, but still not of a level to justify utility. Furtherefforts discussed below in this application will demonstrate substantialsuccess with BW Agents using the inventive compositions.

The mechanisms for the destruction of BW Agents are not as wellunderstood as that of CW Agents. In the case of vegetative bacterialcells and viruses, the kill mechanism is most likely due to theoxidizing effect of oxidizers such as hydrogen peroxide. However,hydrogen peroxide concentrations from 10-20% are required for spore killof Anthrax spores. The spore DNA must be exposed to the oxidizer todetoxify the spore agent. The spore coat protects the DNA and must bebreached to effectively kill the spore agent. A possible mechanismconfirmed in for spore kill is that cationic surfactants can soften anddisrupt the spore coat resulting in breeches through which hydrogenperoxide can enter and attack the spore DNA. (As taught in U.S. Pat. No.6,566,574 incorporated herein by reference.)

Chemical Warfare Agents

Many of the known CW Agents that are likely to pose a threat fromterrorists are nerve agents and mustard. The nerve agents share chemicalsimilarity since they are phosphorus-containing compounds that can bealtered when subjected to nucleophilic attack or oxidation processes.These CW Agents include sarin (O-isopropyl methylphosphonofluoridate),soman (O-pinacolyl methylphosphonofiluoridate), GF or sometimes callcyclohexyl sarin (O-cyclohexyl methylphosphonofluoridate), tabun(O-ethyl N,N-dimethyl phosphoramidocyanidate) and VX (O-ethylS-2-diisopropylaminoethyl methyl phosphonothiolate). The chemicalstructures depicting the similarity of these agents are shown in FIG. 1.If the phosphorous-containing compound is chemically altered bynucleophilic hydrolysis or oxidation, it is detoxified and therebyneutralized as a CW Agent. These CW Agents are only sparingly soluble inwater.

Another common CW Agent is mustard (bis-(2-chloroethyl)sulfide) shown inFIG. 1. Although mustard is chemically quite distinct from the other CWAgents mentioned above, in that it does not share thephosphorus-containing group, it does exhibit chlorine atoms bound tocarbon atoms at both ends of the molecule. These carbon-to-chlorinebonds are also subject to hydrolysis and the central sulfur can beoxidized to sulfoxide or sulfone, thereby rendering the moleculeineffective as a CW Agent. Like the nerve agents, mustard is onlysparingly soluble in water.

Several simulants are well accepted by the US Government for use in CWAgent testing. These simulants have chemical structures and physicalproperties similar to those of the live agents, but they havesignificantly reduced toxicity. The following chemical simulants wereused by the applicants:

G-Agent Simulant:

Diphenyl chlorophosphate (DPCP) (C₆H₅O)₂P(O)Cl

Or Dinmethyl methylphosphonate (DMMP) CH₃P(O)(OCH₃)₂

H-Agent Simulant (Mustard):

2-Chloroethyl phenyl sulfide (CEPS)C₆H₅SCH₂CH₂Cl

VX-Agent Simulant

95% Malathion

CW Agents—Simulant Detoxification with the Prior Art U.S. Pat. No.5,678,238

Micro encapsulation of the selected simulants was conducted with thecommercially available TERRACAP 3000 and 4000 additives (products ofU.S. Pat. No. 5,678,238) in a batch mode to detect simulantdetoxification by alkaline hydrolysis. In an open beaker, the G-Agentsimulant, DPCP, rapidly reacted with the commercial TERRACAP 3000 priorto addition of the TERRACAP 4000 additive to microencapsulate thecontaminate by-products. The extent of reaction was greater than 99.995%(limit of detection 50 ppm by gc-ms) effective within the 5 minutesprior to the quenching by extraction with the aggressive solvent blendof 50/50 methylene chloride/acetone according to the procedure foundbelow. The extremely effective denaturing of the DPCP is due to thealkaline OH⁻ groups in the silica formulation hydrolyzing the P—Cl bond.

The Mustard simulant, CEPS, did not appreciably react under theconditions described above with the commercial micro encapsulationagents TERRACAP 3000 and TERRACAP 4000. The peaks for CEPS were so largethat an accurate measurement was not possible. The levels of reactionwith CEPS was probably less than 50%. The VX simulant, Malathion, wasnot tested because alkaline hydrolysis is known not to be the preferredmethod of detoxification. Although the micro encapsulation technology ofthe prior art was successful for DPCP, it does not have universalapplicability across the spectrum of CB Agents.

Modification of the commercial TERRACAP formulations (U.S. Pat. No.5,678,238) to those of the invention provided substantial improvementsin detoxification effectiveness on the mustard and VX simulants as wellas further improvement on the G-Agent simulant and substantialimprovement in denaturation of the Anthrax simulant.

Development of the Dual-Use, Two-Component Micro Encapsulation System.

From the initial effort at BW Agent micro encapsulation, the results for5-minute detoxification of the anthrax simulant and/or its microencapsulation were high (96%), but due to the extremely high toxicitylevel of the anthrax spore, this result is promising at best andwarrants substantial improvement. Likewise on the CW Agent side, theresult for G-Agents (DPCP) were impressive 99.995% in 5-minutes, butDPCP or G-Agents are easy to hydrolyze. The existing technology was notimpressive for Mustard or VX. Thus, there was a need for substantialimprovement.

Distinguishing Characteristics

There are several novel and unexpected distinguishing characteristics tothe improved micro encapsulation system of the inventive applicationthat allows for optimization as described below:

-   -   1. A two-component system based on an aqueous alkaline silicate        formulation and a slightly acidic aqueous polymer formulation        that interacts to micro encapsulate a substrate on a molecular        level to form a stable, solid, impermeable silica-polymer matrix        that has 100% more capacity than the micro encapsulations system        of U.S. Pat. No. 5,678,238.    -   2. The micro encapsulated matrix is capable of withstanding the        leachable effects of water, stable to aqueous acid or base, and        it will pass the EPA TCLP (method 1311) extraction and        subsequent analysis for environmental waste considerations as        well as the EPA 1320 Multiple Extraction Test for long term        stability.    -   3. Contaminant substrates may be selected from hydrocarbons,        organic chemicals, organometallic chemicals, oxidized metallic        ions, radioactive metal ions, or biological agents that are        miscible or emulsifiable in the system.    -   4. The micro encapsulation system mitigates the characteristic        properties of wastes such as flammability, toxicity,        corrosivity, or reactivity.    -   5. The alkaline silicate formulation may contain surfactants,        emulsifiers, wetting and stabilizing agents, etc. to immobilize        the chemical or biological agent.    -   6. The slightly acidic polymer formulation may contain        surfactants, emulsifiers, wetting, stabilizing agents,        flocculants, and coagulating agents etc. to immobilize the        chemical or biological substrate.    -   7. Either the silicate formulation or the polymer formulation        may additionally contain oxidizing or reducing agents,        hydrolyzing agents, or other nucleophiles, etc. that react to        mitigate the toxicity of CB Agents, TICs or TMs in the        silica-polymer micro encapsulated matrix.    -   8. The system is adaptable. If a component from item 5, 6 or 7        above is not shelf stable in the silicate formulation, it may be        stable and formulated in the polymer formulation. Either the        alkaline silicate formulation or the acidic polymer formulation        may be applied first or both applied almost simultaneously for        micro encapsulation. The flocculation-coagulation interaction is        immediate or it can be retarded if necessary.    -   9. The water-based solutions may be spray applied and the micro        encapsulated material of neutral pH may be removed from the        object by dispersing with a water pressure spray, brushing,        wiping, or vacuuming when wet or dry.

It can be seen from the distinguishing characteristics, there is greatdiversity in the improved micro encapsulation process. However, therewas a great challenge incorporated in the improvements as well that wasnot obvious to one skilled in the art. First, it was desirable toimprove the efficiency of the system which would logically enhance thecost effectiveness for routine clean up of hydrocarbon transportationfluids and yet retain the Distinguishing Characteristics 2, 3 and 4. Themost obvious tactic to improve micro encapsulation efficiency was toincrease the sodium silicate concentration. This was difficult beyond acertain level, because of the existing competition by other componentsfor the water in this highly electrolytic system. For example,concentrated alkaline sodium silicate formulations are of very highelectrolytic strength and are highly hydrophilic. Introduction ofcompeting hydrophilic substances such as in Characteristic 5 to obtain acomposition with micro encapsulation utility as well as shelf stabilitywith out the deleterious problems associated with long-term shelfstability such as splitting into two phases or silicate precipitationwas very difficult.

Furthermore, the same challenge existed with Characteristic 6, becauseit is also a very electrolytic acidic substance and difficult toformulate for shelf stability. Second, inserting the agents ofDistinguishing Characteristic 7 becomes a huge challenge because thesolution equilibrium becomes favorable for system reactions with thecomponent resulting in immediate or delayed precipitation of thesilicate or the polymer formulation. By design, after the microencapsulation reaction has occurred, the detoxification agent isneutralized as well to environmentally acceptable non-hazardoussubstances. Distinguishing Characteristic 8 provides a certain degree offreedom to formulate the certain components or the reactive detoxifyingagent in either the alkaline silica or the acidic polymer formulationalthough there are still limitations.

Although there are unique Distinguishing Characteristics in a microencapsulation system of this invention, the novel utility of thiscomplex “dual-use” system is unexpected and to a large extent definitelynot obvious to one skilled in the art because of all the potentialincompatibilities of the individual components. The compositions of theinvention have shelf stability, are capable of micro encapsulating up to100% more contaminant than the formulations of U.S. Pat. No. 5,678,238,and have the “dual-use” versatility capability of micro encapsulation ofhydrocarbons and chemicals or detoxifying certain CW Agent simulants toless than 10 ppm and anthrax simulant to greater than log 7 efficacy,both in less than five minutes. In addition any by-products ofdetoxification and residual CW Agent simulants are micro encapsulatedand removed from the environment, a characteristic that no otherdetoxification process can claim. The micro encapsulation of theinvention restricts contaminant migration because of the extremely highsurface area inside the porosity where the contaminant is entrapped inthe amorphous silica. Amorphous silica is safe and known to be morestable than crystalline silica, which is a potential carcinogen.

For the first responder, it is critical to decontaminate facilities orequipment to an acceptable level in a matter of minutes in order tolocate and treat casualties. In the restoration scenario, time is ofless importance, but collateral damage, public perception, andre-certification (i.e. complete decontamination) is of greaterconsequence. A common formulation effective against all CB Agents mustbe suitable for use on a wide variety materials and surfaces.Additionally, the neutralization formulation must be able to be rapidlydeployed in large quantities by first responders to effectivelyneutralize CB toxants while remaining relatively harmless to both peopleand property. The formulation of the present invention accomplishesthese goals for civilian and military applications because it hasdual-use capability. The benefits of the invention follow since it is:

-   -   1. Nominally, a two-component composition used for routine micro        encapsulation of hydrocarbon fuels and oils,    -   2. Rapidly modified to a three-component micro encapsulation        composition that can provide rapid detoxification of highly        hazardous substances such as CB Agents and TICs,    -   3. Adaptable to solid support, bulk, aerosol and vapor phase CB        Agent contamination,    -   4. Amenable to minimal health and collateral damage,    -   5. A minimal logistics support requirement technology,    -   6. Capable of producing no liquid by-products and no lasting        environmental impact    -   7. Relatively inexpensive.

Components of the Inventive Formulations

Sodium silicate is a complicated system of various molecular weightsilica polymers in an alkaline solution. Aside from requiring a certainminimum amount of buffered alkalinity, sodium silicate has no definitechemical combining numbers. When sodium silicate is acidified to a pH ofless than about 10, the sodium silicate is converted partially tosilicic acid. Silicic acid exists at these alkaline pH's as it is such aweak acid. Instead of precipitating and making silica, SiO₂, the silicicacid remains hydrated and forms a three-dimensional network in trappingthe solvent water. This network is a gel since both phases arecontinuous.

Silicates which can be used for the compositions and processes of thepresent disclosure are the water soluble silicates which form silicatepolymer chains or gel upon acidification. The preferred silicates arethose of the alkali metals, especially sodium or potassium andcombinations thereof. These silicates are commercially available as drypowders or concentrated aqueous solutions having in the range of fromabout 38 to 55 parts solids per hundred parts of solution and a pH inthe range of from 10.5 to 13. Preferably, the water-soluble silicates,that are employed in the present disclosure have a molar ratio ofsilicon dioxide to alkali metal oxide in the range of from about 0.5:1to about 3.5:1 and the alkali metal is sodium, potassium, and mixturesthereof. Most preferably, the ratio should be from about 3:1 to about3.5:1. The concentration of sodium silicate solution in the microencapsulation solution can vary over a wide range from 10 percent to 95%and preferably between 20 to 60 percent.

Anionic surfactants are surface-active compounds consisting of ahydrophobic alkyl chain and a hydrophilic group. Anionic surfactants arenegatively charged in aqueous solutions due to the presence of asulfate, sulfonate, carboxylate or phosphate group. They are watersoluble and ionize to produce a negative charge in aqueous solution.Anionics are generally credited with excellent detergent cleaningproperties. Common anionic surfactant groups are the acids, or sodium,potassium or ammonium salts of alkyl carboxylates (soaps), alkyl ethercarboxylates, alkyl benzene sulphonates, alkyl ether phosphates, alkylether sulphates, alkyl naphthalene sulphonates, alkyl phosphates, alkylphenol ether phosphates, alkyl phenol ether sulphates, alpha olefinsulphonates, aromatic hydrocarbon sulphonates, condensed naphthalenesulphonates, di-alkyl sulphosuccinates, fatty alcohol sulphates,mono-alkyl sulphosuccinates, alkyl sulphosuccinamates, and naphthalenesulphonates among others.

Representative examples of selected anionic surfactants useful in theinventive sodium silicate formulation might be sodiumdodecylbenzenesulfonate, triethanolamine dodecylbenzene sulfonate,isopropylamine dodecylbenzene sulfonate, sodium capryl sulfonate, sodiumC₁₄₋₁₆ alpha olefin sulfonate, ammonium lauryl sulfate, ammonium laurylether sulfate (EO=3), sodium 2-ethylhexyl sulfate, and alkylpolyethersulfonates (R=8-15, EO=3-15). These anionic surfactants may beincorporated in the sodium silicate formulations of the invention atconcentrations ranging from 0.01 to 15 weight percent. More preferably,anionic surfactants may be incorporated in the sodium silicateformulations of the invention at concentrations ranging from 0.1 to 6weight percent.

Nonionic surfactants are surface-active compounds with hydrophobic andhydrophilic groups. Nonionic surfactants do not ionize in solutionbecause they have no electrical charge. They are mixtures of homologousstructures composed of alkyl chains that differ in the number of carbonsand with hydrophilic groups that differ in the number of ethylene oxide(ethoxylate, EO) propylene oxide (propoxylate, PO) and butylene oxide(butoxylate, BO) units. The most common are alcohol ethoxylates preparedby attaching ethylene oxide molecules to a water-insoluble molecule.Depending on the number of ethylene oxides and the number of carbonatoms, the nonionics can be classified as a wetting agent, a detergent,or an emulsifier. Common nonionic surfactant groups are the alkylpolysaccharides, alkyl amine oxides, alkyl glycosides, alkanolamides,fatty acid glucose amides, block copolymers, and ethoxylates of castoroil, alkyl alcohols, alkylphenols, ether amines, alkanolamides, ethyleneglycol esters, alkyl amines, random copolymers, sorbitan esters,alkylcarboxylic acids, and alkyl amines.

Nonionic surfactants are often difficult to formulate in the highlyelectrolytic sodium silicate solutions of the invention. They oftenresult in unstable two-phase systems such as the preferred compositionof U.S. Pat. No. 6,436,884 which are not very useful. Nonionicsurfactants normally require a substantial amount of a hydrotropesurfactant in sodium silicate solutions to provide solvative assistance.Likewise, the T-MULZ surfactant, an anionic blend from Harcross, used inthe representative composition of U.S. Pat. No. 5,478,389 is notcompatible resulting in a two-phase system. Phosphate esters are oftendifficult to solubilize in highly electrolytic sodium silicate solutionswithout a hydrotrope.

Representative examples of selected nonionic surfactants useful in theinventive sodium silicate formulation might be ethoxylated derivativesof nonylphenols (EO=7-11), alkyl alcohols (R═C₉-C₁₁, EO=8), cocamide(EO=6), coconut diethanolamide, alkylpolyglucoside,bis-(2-hydroxyethyl)isodecylcyclohexylpropylamine, stearyl ether(EO=23), isodecyloxypropylamine (EO=5), N,N-dimethyl-N-octylamineN-Oxide, and bis-(2-hydroxyethyl)(C₁₂₋₁₅)alkyloxypropyl amine oxide.These nonionic surfactants may be incorporated in the sodium silicateformulations of the invention at concentrations ranging from 0.01 to 10weight percent. More preferably, anionic surfactants may be incorporatedin the sodium silicate formulations of the invention at concentrationsranging from 0.1 to 6 weight percent.

Amphoteric surfactants are surface-active compounds with both acidic andalkaline properties. Amphoteric surfactants include two main groups,i.e. betaines and real amphoteric surfactants based on fatty alkylimidazolines structures during the synthesis of some of thesesurfactants. The key functional groups in the chemical structures ofamphoteric surfactants are the semi quaternized nitrogen and thecarboxylic group as shown below.

R—C(═O)NHCH₂CH₂N(CH₂CH₂OH)CH₂CH₂CO₂ ⁻Na⁺  Amphoteric Surfactant

Betaines are characterized by a fully quaternized nitrogen atom and donot exhibit anionic properties in alkaline solutions, which means thatbetaines are present only as ‘zwitterions’ as shown below:

R—N⁺(CH₃)₂CH₂CO₂ ⁻  Betaine Surfactant

Imidazolines contain the real amphoteric surfactants that form cationsin acidic solutions, anions in alkaline solutions, and ‘zwitterions’ inmid-pH range solutions. The mid-pH range (isoelectric range) in whichthe surfactant has a neutral charge is compound specific and depends onthe alkalinity of the nitrogen atom and the acidity of the carboxylicgroup. Amphoteric surfactants are used in personal care products (e.g.hair shampoos and conditioners, liquid soaps, and cleansing lotions) andin all-purpose and industrial cleaning agents. Besides acting as mildsurfactant, the amphoteric surfactant may improve the mildness ofespecially anionic surfactants. Common amphoteric surfactant groups arethe alkyl amphoacetates and proprionates, alkyl Ampho(di)acetates, anddiproprionates, alkyl amphohydroxyalkyl sulfonates, alkylamido betaines,alkyl betaines, alkyl hydroxysultaines, iminodipropionates, andalkylimidazolines precursors to the amphoacetates and proprionates.

Representative examples of selected amphoteric surfactants useful in theinventive sodium silicate formulations might be disodiumcocoamphopropionate, C₅₋₉ alkylamphoproprionate, sodiumcocoamphopropionate, octyliminodipropionic acid, sodium beta-alanineN-(2-carboxyethyl)-N-[3-(decyloxypropyl)], alkyl imidazoline propionateester, sodium lauriminodipropionate, disodium cocoamphodiacetate, sodiumcocoamphoacetate and sodium caprylamphopropionate. These amphotericsurfactants may be incorporated in the sodium silicate formulations ofthe invention at concentrations ranging from 0.01 to 15 weight percent.More preferably, anionic surfactants may be incorporated in the sodiumsilicate formulations of the invention at concentrations ranging from0.1 to 6 weight percent.

Hydrotropes are used as coupling agents to solubilize the waterinsoluble and often incompatible functional ingredients of a cleaningproduct. Some hydrotropes are not surfactants but are used to solubilizecomplex formulations in water, but some anionic surfactants havehydrotroping capacity. They function to stabilize solutions, modifyviscosity and cloud-point, limit low temperature phase separation andreduce foam. Hydrotropes are amphiphilic substances composed of both ahydrophilic and a hydrophobic functional group. The hydrophobic part ofthe molecule is usually a benzene or alkyl benzene substituted apolarsegment. The hydrophilic, polar segment is an anionic sulfonate group orgroups accompanied by a counter ion (i.e., ammonium, calcium, potassiumor sodium). It is often impossible to incorporate sufficient quantitiesof surfactants into the detergent system without the use of hydrotropes.Common hydrotropes are salts of xylene sulfonates and alkyl naphthalenesulfonates or alkylated diphenyl oxide disulfonates. Certainalpha-olefin sulfonates and alkyl ether sulfates and phosphate estersare anionic surfactants with hydrotroping ability as well as gooddetergents, emulsifiers or wetting agents.

Representative examples of selected hydrotropic surfactants useful inthe inventive sodium silicate formulation or the polymer flocculantformulation might be sodium xylene sulfonate, alkyldipenyl oxidedisulfonate (R═C₆₋₁₆). Many of the other surfactants often havehydrotroping properties. The solubility of phosphate esters is morelimited than sulfonates in the highly electrolytic complex formulationsof the invention. These hydrotrope surfactants may be incorporated inthe sodium silicate formulations of the invention at concentrationsranging from 0.1 to 15 weight percent. More preferably, anionicsurfactants may be incorporated in the sodium silicate formulations ofthe invention at concentrations ranging from 0.5 to 10 weight percent.

Cationic surfactants are surface-active compounds with at least onehydrophobic alkyl chain and a hydrophilic group carrying a positivecharge. Quaternary ammonium compounds are characterized by a positivelycharged quaternary nitrogen atom. Commercial raw materials are normallyderived from natural oils which implies that homologous mixtures ofsurfactants with different alkyl chain lengths are used in the mostproducts. In household products, cationic surfactants are primarilyapplied in fabric softeners, hair conditioners, and other hairpreparations. Other applications of cationic surfactants includedisinfectants, biocides, emulsifiers, wetting agents, foaming agents,and processing additives. Because of their positive charge, cationicsurfactants absorb strongly to the negatively charged surfaces ofsludge, soil and sediments. Anionic and cationic surfactants usedtogether in the same formulation are frequently incompatible. Commoncationic surfactant groups are the alkyl amidopropylamines, alkyl esterammonium salts, alkyl imidazoline derivatives, quaternised amineethoxylates and quaternary ammonium compounds such as alkyltrimethylammonium salts, dialkyldimethylammonium salts,alkyldimethylbenzylammonium salts.

Representative non-limiting examples of selected cationic surfactantsuseful in the inventive polymer setting formulation might be cetyltrimethyl ammonium chloride, lauryl dimethyl benzyl ammonium chloride,cetyl pyridinium chloride and isodecyloxypropyldihydroxyethylmethylammonium chloride. These cationic surfactants may be incorporated in theacidic polymer formulations of the invention at concentrations rangingfrom 0.01 to 15 weight percent. More preferably, cationic surfactantsmay be incorporated in the acidic polymer formulations of the inventionat concentrations ranging from 0.1 to 6.0 weight percent.

Polycarboxylates are homopolymers of acrylic acid or copolymers ofacrylic acid and maleic anhydride, generally as sodium salts. They actas anionic surfactants. A representative example of a polycarboxylatemight be Tersperse 2735 available from Huntsman Chemical Company in SaltLake City, Utah or Sokalan CP-10 from BASF Corporation in Mount Olive,N.J. These polymers may be incorporated in the sodium silicateformulation of the invention to provide detergency and emulsification atconcentrations ranging from 0.01 to 4.0 weight percent and morepreferably from 0.1-2.0 weight percent.

Block copolymers consisting of long chains of EO and PO units are oftenused as nonionic surfactants. The block copolymers do not contain ahydrophobic moiety based on a fatty alcohol. Instead, the PO unitsfunction as the hydrophobic part establishing surface-active propertiesin combination with the more hydrophilic EO units. These products havelimited solubility in the inventive sodium silicate formulations.However, the alkoxylated polyamine Poloxamine 904 known as Tetronic 904from BASF Corporation is useful in the inventive sodium silicateformulation. These polymers may be incorporated in the sodium silicateformulation of the invention to provide detergency and emulsification atconcentrations ranging from 0.01 to 2.0 weight percent and morepreferably from 0.1-1.0 weight percent.

Co-solvents are frequently used in aqueous surfactant cleaningformulations to impart solubility of the components in the formulationand aid in enhancing the desorbtion of oily substances by dissolvingthem in the system. Co-solvents also work in conjunction withhydrotropes to solubilize surfactants that are difficult to retain inthe solutions of the inventions. Examples of the most common co-solventsare glycols, polyglycols, and the many glycol ethers and glycol etheracetates available in the industry. However, the presence of theseco-solvents in the inventive formulations may become a major contributorto Chemical Oxygen Demand (COD) because the co-solvents are moreextractable (EPA 1311 TCLP) from the micro cell than the othersurfactant additives. If COD is not an issue, these solvents may beincorporated in the formulated sodium silicate solution of the inventionat concentration levels of 0.1 to 15 weight percent. More preferably, cosolvents may be incorporated in the sodium silicate formulations of theinvention at concentrations ranging from 1 to 6 weight percent.Incorporation of co-solvents often reduces the need for hydrotropes.Co-solvent use may be more economical than hydrotropes to providestability in a formulation, however it is often best to formulate astable system without either component. Due to the inert, solid natureof the micro encapsulated substance of the invention, the CODcontribution to the environment is extremely low compared to otherenvironmental technologies.

Polymers are useful in the acidic solution as a fixation or flocculationagent to assist in precipitating and binding the contaminant in thesilicate matrix. Such polymers might be selected from any of thepolyamines, polyacrylamides, polyimines and polydially dimethyl ammoniumchloride (DADMAC) available from BASF or Kemira (formerly CYTEC) aspaper sizing agents or flocculants. The concentration of the polyamine,polyimine and polyDADMAC polymers is between 0.01-4 percent by weightand preferably between 0.12 percent by weight.

The inorganic agents used for coagulation or setting in the acidicpolymer formulation are chosen from the common agents such as calciumchloride and aluminum chlorohydrate. Numerous other coagulation agentscould be used in the acidic polymer formulation of the invention suchas: inorganic Ca, Mg, Na, K, Zn and Al salts of hydroxides, oxides,phosphates, sulfates borates, or carbonates; common inorganic mineralacids, common organic acids, organic esters, amides, carbonates, glycolsor silanes and silicofluorides. The concentrations may range between0.5-50 weight percent and more preferably between 3 to 30 weightpercent.

The pH of the acidic polymer formulation may be controlled by theaddition of an acid. The acids may be chosen from the mineral acids suchas concentrated hydrochloric acid, sulfuric acid, phosphoric acid andthe like or they may be chosen from organic acids such as acetic acid,oxalic acid, glycolic acid or any of the commonly used acids used toalter the pH of a system. A preferred acid being concentrated phosphoricacid used in the concentration range of from 0.1 to 10 weight percent.

Realize that all in all of the possible combinations and concentrationsof surfactants or polymeric surfactants used for detergency,emulsification, wetting or hydrotroping and other additives for solvencyin the presence of sodium or potassium silicate for the formulation ofthe invention, some will be stable and useful while others will be lesspreferred because of limited compatibility of the components in theformulation most often resulting in premature silica precipitation orlack of shelf stability resulting in a two-phase solution. Likewise, ofall the possible combinations and concentrations of surfactants,polymers, coagulants, acids and the like for generating the solidmicrocapsules of the invention, some will be stable and useful whileothers will be less preferred because of limited compatibility of thecomponents in the formulation resulting in premature precipitation ofthe setting agent(s) or lack of shelf stability resulting in a two-phasesolution. Furthermore, of all the possible combinations andconcentrations of the components of the silicate formulation and thepolymer flocculation formulation, some will provide an excellent microencapsulation of the contaminant while others will be less desirable dueto efficiency, contaminant emulsification, syneresis of water or theliquid contaminant, water leachability, and the like. The microencapsulation formulations of the invention are novel and provideunexpected performance in light of any previous prior art. Theformulations of the micro encapsulation invention show unexpectedstability to the detoxification agents when incorporated into theformulation as shown later in the spectral analysis of the byproducts ofsimulant oxidation.

Micro Encapsulation Process of the Inventive Composition forHydrocarbons and Chemicals

The micro encapsulation process of the invention for hydrocarbons andchemicals (without detoxification) occurs on a molecular level to form acomplex inert amorphous silica matrix. The first component of theinvention is an aqueous, alkaline, sodium silicate formulation to desorband emulsify the contaminant into micelles. Specific surfactant packagescan be tailored for specific treatments.

The second component of the micro encapsulation process of the invention(without detoxification) is a slightly acidic, aqueous, polymerformulation that rapidly reacts with the alkaline silicate formulationcontaining the contaminant to complete the micro encapsulation process.Within 10 seconds, microencapsulation begins and is observed asflocculated-precipitated agglomerates of polymer-silicate material withcalcium-aluminum salts that contains the contaminant species inside thein-penetratable silica-polymer matrix. As time approaches one minute,the precipitated agglomerates firm up into a wet, fine-like sandy paste.The pH of the micro encapsulated material is in the neutral range. Thismicro encapsulation process removes the hazardous characteristics ofthis waste, such as ignitability, corrosivity, reactivity and toxicity.The micro encapsulated material is resistant to water penetration andleaching, and offers impressive long-term stability.

Since the first formulation of the invention is alkaline, the secondformulation of the invention is acidic, and the desired pH of theresulting micro encapsulated wet composition targeted to be in the rangeof 6.5-7.5. The level of acidity of the acidic polymer formulation isdesigned to meet this requirement by making slight adjustments in theacid concentration.

In one application embodiment, the inventive micro encapsulationformulations may be applied by bulk addition, spraying or misting thesilicate formulation on a contaminant coated surface. Mixing is vital tothe quality of the micro encapsulate. The silicate formulation isdesigned to rapidly emulsify the hydrocarbon and optimally, the energyfrom spraying the silicate formulation onto the contaminant providesthat energy. If this amount of energy is insufficient to form a milkyemulsion, then a certain level of mechanical or manual agitation isnecessary to complete the emulsification. Then the second acidic polymercomponent is applied immediately after emulsification by bulk additionor spraying onto the emulsified silicate contaminant mixture. Onceagain, at this stage mixing is vital to providing the optimum microencapsulation result in the form of a homogeneous paste. Theapplications system consists of a portable unit with two tanks or drumsof the two non-toxic aqueous formulations. Two individual spray systemsare required because the two individual formulations when mixed togetherwithout the contaminant will form a micro encapsulated mass.

In another embodiment, the inventive micro encapsulation formulationsmay be diluted prior to application by bulk addition, spraying ormisting on a contaminated soil as the soil is being mixed and processedthrough a device such as a pug mill. Water dilution of the twoformulations up to one part formulation to two parts water prior toapplication allows for more efficient surface coverage of the soilwithout affecting the micro encapsulation performance. If thecontaminant is spilled on a hard surface, the two formulations mayeffectively be diluted up to one part formulation to one part waterwithout significantly affecting the resultant micro encapsulate. Sinceminor amounts of dilution do not effect performance, it is possible toapply the inventive micro encapsulation process on water wet surfaces orduring periods of light rainfall. However, this is not to claim that theprocess can treat hydrocarbon spills on bodies of water.

The potential customers that may benefit from this technology is broadand diverse. They range from DoD, DOE, FAA, DOT, emergency responseentities and any industrial manufacturing, transportation, storage orservice industry that manufactures, consumes or handles hydrocarbons orchemicals and residential consumers.

CW Agent Detoxification by Nucleophilic Hydrolysis

Chemical hydrolysis reactions are commonly of two types: acid andalkaline. Acid hydrolysis is of negligible importance for CW Agentdecontamination because the acid hydrolysis rate of most chemical agentsis slow and adequate acid catalysis is rarely observed according toWagner and Yang (U.S. Pat. No. 6,245,957 B1). Alkaline hydrolysis isinitiated by the nucleophilic attack of the hydroxide ion on thephosphorus atoms in VX and the G-Agents. The alkaline hydrolysis rate isdependent on the chemical structure and reaction conditions. The rateincreases sharply at alkaline pH values higher than 8.

G-Agents have a phosphoryl fluoride bond that is expected to be verysimilar in chemical reactivity to the phosphoryl chloride bond indiphenyl chlorophosphate (DPCP) simulant. Tabun, with a —CN group, mightalso behave similar to the —F or —Cl group. Halide and cyanide ions areknown to be fairly good leaving groups in nucleophilic hydrolysisreactions. Therefore, G-Agent hydrolysis is rapid and DPCP, the simulantthat most closely structurally related to the G-Agents, should reactrapidly as well. If the simulant is acidic, such as DPCP, the first stepin the neutralization is nucleophilic attack at the phosphorus atom andsubsequent displacement of the chloride ion most likely via an S_(N)2type mechanism as represented in Equation 1. One equivalent of analkaline OH⁻ nucleophile is required. The resulting products are sodiumdiphenylphosphonate and HCl. The HCl produced would require anotherequivalent of alkaline nucleophile for neutralization. Overall, twoequivalents of nucleophile would be required for the firstneutralization step according to the reaction shown in Equation 1.

2-Chloroethylphenyl sulfide (CEPS), C₆H₅SCH₂CH₂Cl, is much differentfrom DPCP mechanistically in terms of nucleophilic reactivity. Thereaction is most likely considered an S_(N)1 nucleophilic mechanism withanchimeric (neighboring group) assistance. The first hydrolytic stepwith CEPS is the neighboring group nucleophilic attack of the sulfide Son the β-carbon to form an intermediate sulfonium ion as shown inEquation 2 (Giletto et. al. U.S. Pat. No. 6,569,353 and Curry et. al.U.S. Pat. No. 6,692,694). The reactant and the ion pair are inequilibrium and

the observed reaction rate decreases with increasing chlorideconcentration. The hydroxyl nucleophile attacks the sulfonium ion at oneof the ring carbons, opening the ring to give 2-hydroxyethylphenylsulfide and sodium chloride.

Nucleophilic hydrolysis of VX is known to occur slowly according toTadros and Tucker (U.S. Pat. No. 6,566,574). The hydrolysis productsbelow pH 10 include EA2192, which is nearly as toxic as VX itself andlonger lived. Thus, hydrolysis-based decontamination schemes are not aneffective option against VX. Oxidation at the nitrogen and sulfur atomsis the method of choice for VX decontamination. Malathion was chosen asthe simulant for VX and oxidation as the preferred destruction method.Hence, nucleophilic hydrolysis of VX was not attempted.

CW Agent Detoxification by Oxidation

Nucleophilic hydrolysis is only one mechanism for CW Agentdetoxification. Oxidation is perhaps even more prominent. Bleaches andperoxides have been known for years to detoxify CW Agents. Numerousoxidant formulations have been used by the military for CW Agents suchas super tropical bleach (93% calcium hypochlorite and 7% sodiumhydroxide), potassium permanganate, hydrogen peroxide, and others.

Percarbonates

Precedence is found in the patent literature for the use ofpercarbonates, perborates and persulfates as improved active oxidizers(Giletto U.S. Pat. No. 6,569,353, Curry et. al. U.S. Pat. No. 6,692,694and Tadros et. al. U.S. Pat. No. 6,566,574). More recently, Oxone (amixture of KHSO₅, KHSO₄ and K₂SO₄ from Du Pont) has been used. Of theoptions available, it is the applicant's intent to focus more on thechoice of sodium percarbonate and peracetic acid as the choice ofoxidants to integrate into the inventive compositions.

Oxidizers are usually not shelf stable substances and when in contactwith most other chemicals, they either react or decompose to produceoxygen. Therefore, oxidizers must be added to the inventive formulationjust prior to use. This is actually beneficial, because it allows thebase two-component formulation to be used for multi-purpose facilityclean up and when a detoxifying formulation is required, the activeagent may simply be mixed into the base formulation when needed. Forexample, sodium percarbonate may be added to the fully formulated sodiumsilicate composition since sodium percarbonate requires an alkalinemedium and peracetic acid may be added to the fully formulated acidicpolymer formulation since it requires an acidic medium for oxidation. Ifthe alkaline silicate contains the detoxifying agent, it is added to thecontaminant first, then the acidic polymer formulation without adetoxifying agent is added second for micro encapsulation purposes.Likewise, if the acidic polymer formulation contains the detoxifyingagent, it is added to the contaminant first, then the alkaline silicateformulation without a detoxifying agent is added second for microencapsulation purposes.

Sodium percarbonate (2Na₂CO₃.3H₂O₂) is a solid bleaching agent used inpowdered laundry detergents and other cleaning products. Itseffectiveness comes from the formation of the alkaline percarbonate ionand hydrogen peroxide in aqueous solutions as shown in Equation 3.Sodium percarbonate solutions remain active for 5 to 6 hours, afterwhich they become inactive and are harmless. Likewise, when the acidicpolymer component is added to the sodium silicate formulation withsodium percarbonate, any excess sodium percarbonate is neutralized andthe by-products are harmless.

2Na₂CO₃.3H₂O₂+H₂O→2HCO₄ ⁻+H₂O₂+H₂O+2Na⁺  Equation 3

The reaction stoichiometry with the simulants suggests the VX simulant,Malathion, would require the most additional oxygen for decomposition. A12 percent by weight sodium percarbonate solution was prepared andaliquots of this solution were used in order to have a minimum of atwo-fold excess percarbonate and hydrogen peroxide for initial simulanttesting.

Peracetic Acid

Peracetic acid (CH₃COOOH) is a very strong oxidizing agent with astronger oxidation potential than chlorine or chlorine dioxide as shownin Table 1. Peracetic acid is a clear, colorless liquid

TABLE 1 Oxidation Capacity of Various Oxidizers Oxidizer EV* Fluorine3.05 Ozone 2.07 Peracetic Acid 1.81 Hydrogen Peroxide 1.78 PotassiumPermanganate 1.68 Chlorine Dioxide 1.57 Chlorine 1.36 SodiumHypochlorite (1) 1.36 Bromine 1.07 *electron volts (1)http://www.ams.usda.gov/NOP/NationalList/TAPReviews/PeraceticAcid3.pdfChlorine bleach is a secondary substrate of chlorine that is most activeat lower pH.with no foaming capabilities, and has a strong pungent acetic acid(vinegar) odor. Peracetic acid is a mixture of acetic acid and hydrogenperoxide in an aqueous solution (Equation 4). It is a very strongoxidizing agent and has stronger oxidation potential than chlorine orchlorine dioxide.

Peracetic acid's primary use is as a sanitizer and disinfectant forfood. Although peracetic acid is not explicitly listed as GRAS by FDA,it arguably benefits human health by controlling food-borne pathogens(J. P. Cherry, “Improving the Safety of Fresh Produce WithAntimicrobials”, Food Technology, 53: 54ff, 1999) and is widely used.When the sodium silicate component is added to the acidic polymercomponent containing peracetic acid for the purpose of microencapsulation, any excess peracetic acid is neutralized and theby-products are harmless.

The most common commercial concentrations are between 5 to 15 percent.Peracetic acid has been used primarily as a sanitizer and watertreatment compound in food and beverage processing, as a successfuloxidizer for removing biofilms from food contact surfaces without afinal rinse, as an outstanding odor suppressant, and as a bleachingagent. Although relatively new to the US for use in municipal watertreatment, peracetic acid is an outstanding disinfectant, usedsuccessfully for over 15 years in other countries, to replacechlorination and as a UV disinfection supplement in secondary sewagetreatment plants. Another of peracetic acid's unique advantages, is itsvery potent ability to oxidize sulfide molecules at all pH valuesassociated with wastewater uses. The reaction is instantaneous andyields sulfate, which cannot combine with other entities to form furthernuisance compounds. Disulfide molecules constitute the proteins in sporecoats; hence the success described later in the examples of completedenaturation of B. atrophaeus and the sterne strain of B. anthraxis withperacetic acid. The reason for the excellent and rapid antimicrobialeffect of peracetic acid is perhaps due to its specific ability todiffuse through the cell membrane. The high oxidation potential of theproduct results in the irreversible destruction of the system inside thecell with the result that the microorganism is destroyed. Thus,peracetic acid is a very broad-spectrum anti-microbial (bactericidal,fungicidal, sporicidal and viricidal) agent.

Peracetate Generation In Situ

The peracetate ion may be generated in situ using the peroxycarbonateion with a bleach activator in a perhydrolysis reaction. Bleachactivators may be esters, amides, imides, or anhydrides. They must havea perhydrolyzable acyls and a good leaving group such asoxybenzenesulfonate. Selection may vary with the advantages ordeficiencies of particular bleach activators, such as low compatibilitywith additional components, limited storage stability, low massefficiency, surfactant incompatibility, lack of biodegradability, andhigh cost. Bleach activators include: nonanoyloxybenzene sulfonate(NOBS) (Proctor & Gamble), sodium nonanoyloxybenzene sulfonate (SNOBS),tetraacetylethylenediamine (TAED), tetracetyl glycoluryl (TAGU),pentaacetylglucose (GAG), lauroyloxybenzene sulfonate (LOBS) anddecanoyloxybenzenecarboxylic acid (DOBA). (U.S. Pat. No. 6,369,288, D.M. Davies et al J. Chem. Soc., Perkin Trans. 2, 1998)

The activator reacts with hydrogen peroxide or a hydrogen peroxidesource such as the peroxycarbonate ion in alkaline aqueous solution, toform a peracid, typically a percarboxylic acid RC(O)OOH or its anion,with loss of a leaving-group, L, or its conjugate acid, LH. (Equation10)

R—C(═O)-L+HCO₄ ⁻→R—C(═O)—OOH+LH+CO₂  Equation 10

Since the peracetate anion generated via peroxycarbonate and a bleachactivator is very similar to the peroxycarbonate anion, the mechanisticselectivity should be the same except further alkaline hydrolysis to thedivinyl sulfoxide and divinyl sulfone may not occur.

Another attractive bleach activator is acetylsalicylic acid (aspirin)using sodium perborate as the peroxy compound (Kralovic et. al. U.S.Pat. No. 5,116,575 and U.S. Pat. No. 5,350,563) as shown in Equation 3.The uniqueness of this combination is that the by-products of thereaction between acetylsalicylic acid and sodium perborate are sodiummetaborate, an inorganic corrosion inhibitor and salicylic acid, anorganic corrosion inhibitor. Peracetic acid generated from aspirin andsodium perborate monohydrate are compatible with the slightly acidic,aqueous, polymer formulation of the invention. Peracetic acid generationby this means requires only a mater of a few minutes and provides a highlevel of CB Agent simulant or TIC detoxification prior to microencapsulation. The advantage is the starting materials are safer tohandle, transport with only minimal restrictions, and have good shelflives.

o -HO(O═C)C₄H₆O(C═O)CH₃+H₂O+NaBO₃→NaBO₂+CH₃(C═O)OH+ o-HO(O═C)C₄H₆OH  Equation 3

For either peracetic acid or in situ peracetic acid generation, fieldapplication could be as simple as adding a predetermined amount ofperacetic acid or each of the solid precursors, such as aspirin andsodium perborate, together in water and add to the acidic polymer microencapsulation component and mix.

In summary, there are several options or methods for generating therequired peracetic acid in situ as a part of the inventive process.Generation at the time of need would be a preferred solution in that itwould improve the logistics and shelf life of the detoxificationadditive.

G-Agents

The G-Agents most likely method of detoxification is nucleophilichydrolysis. While G-Agents are decontaminated by a variety of oxidativesolutions, they all are capable of alkaline hydrolytic neutralizationand there is no evidence of exclusively oxidative decontaminationreactions for G-Agents.

Competing hydrolyses of GB (Equation 5) with OH- andOOH-(peroxocarbonate) yields non-toxic isopropyl methylphosphonic acid(IMPA) and peroxy-IMPA respectively. The peroxy-IMPA is an intermediate,decomposing to IMPA with further consumption of H₂O₂ and evolution ofO₂.

Mustard

In aqueous alkaline solutions, sulfur mustard simulant CEPS is quicklyhydrolyzed to the alcohol in a two-step reaction via Equation 2. In thepresence of alkaline sodium percarbonate oxidant, the sulfur is mostlikely oxidized to the alcohol sulfoxide and/or sulfone as shown inEquation 6. The active oxidant species is thought to be thehydroperoxide anion HO₂ ⁻¹.

When peracetic acid is used as the oxidizing agent in the acidic microencapsulation component, the CEPS is oxidized directly to thecorresponding chloro sulfoxide and chloro sulfone products by the samehydroperoxide ion.

Mustard sulfoxide is extremely stable to hydrolysis and slightly toxic.Further oxidation under more severe conditions forms mustard sulfone, arelatively non-toxic compound Reference: (Toxicological Profile forSulfur Mustard-Update, US Department of HHS September 2003. Thisdocument references Clark 1989; Price and Bullitt 1947; Rosenblatt1975). Both the sulfoxide and sulfone are water soluble, different fromMustard. Mustard sulfone and mustard sulfoxide easily eliminates HClunder alkaline conditions to give divinylsulfone, which is highly toxic,and divinylsulfoxide, respectively, hence a preference for acidicoxidation mechanism.

Mustard oxidation with the peroxycarbonate ion (Equation 7) occursquantitatively to the non-vesicant sulfoxide (HDO) instead of furtheroxidation to the sulfone (HDO₂). Contrary to Clark, Price and Bullitt(1947), and Rosenblatt (1975), Wagner (U.S. Pat. No. 6,245,957 B1)(Complete references at the front of this document) claims the sulfoxideis preferred to the sulfone, which is nearly as

Cl—CH₂CH₂—S—CH₂CH₂—Cl→Cl—CH₂CH₂—S(═O)—CH₂CH₂—Cl  Equation 7

potent a vesicant as mustard. Avoidance of sulfone production is ofprimary concern for an oxidant-based decontaminant, and thedecontamination with percarbonate provides this critical selectivity.However, it is likely at high pH mustard undergoes a nucleophilichydrolysis reaction to the corresponding alcohol prior to oxidation tothe sulfoxide.

VX-Agent

VX-Agent is similar in structure and biological activity to somecommonly used insecticides, such as Malathion, carbamates such as Sevin,and medicines such as Mestinon, Neostigmine and Antilirium. Wagner andYang (U.S. Pat. No. 6,245,957 B1) claim that the reaction ofpercarbonate with VX provides a perhydrolysis mechanism as shown in thebelow (Equation 8).

C₂H₅O(CH₃—)P(═O)SCH₂CH₂N(CH(—CH₃)₂)₂+HCO₄⁻→C₂H₅O(CH₃—)P(═O)O⁻+⁻O₃SCH₂CH₂N(CH(—CH₃)₂)₂  Equation 8

Exclusive cleavage of the P—S bond occurs to yield non-toxic ethylmethylphosphonic acid (EMPA), thus preventing formation of highly toxicEA-2192 (S-2-(diisopropylamino)ethyl methyl-phosphonothioc acid), whichoccurs via exclusive P—O bond cleavage. The cleaved thiol is oxidized tothe sulfonate, consuming further hydrogen peroxide.

With Malathion as the simulant, the oxidants are envisioned to reactwith the P—S bond as shown in Equation 9 to form an intermediate. Oncethe S atom is oxidized, hydrolysis is very rapid to form a malonatesulfonate salt and O,O-dimethyl phosphorothioate salt.

Example 1 Alkaline Sodium Silicate and Acidic Polymer MicroEncapsulation Formulations

The compositions shown in Table 2 are representative of the sodiumsilicate formulations of the invention using different surfactantmixtures. All formulations perform well in the micro encapsulation ofhydrocarbons and chemicals. Entries 1-5 are examples of sodium silicatemicro encapsulation formulations of the invention. Entry 7 was thesilicate formulation used for nucleophilic hydrolysis of CB Agents andoxidation using sodium percarbonate. Entry 6 is a preferred sodiumsilicate formulation for micro encapsulation and detoxification withperacetic acid for CB Agents followed by micro encapsulation. Thecompositions and manufacturers of the components are provided in Table2A. The order of addition to prepare the sodium silicate formulations ofthe invention follows: Usually a small amount of the water (25 weightpercent) is added to the anionic surfactant followed by the nonionicsurfactant and a hydrotrope if required. The remaining water is added tothe mixture and the sodium silicate is added last. Stirring is requiredto insure all components go into solution.

TABLE 2 Examples of Sodium Silicate Formulations of the Invention Entry1 Entry 2 Entry 3 Entry 4 Entry 5 Entry 6 Entry 7 Entry 8 Component Wt %Wt % Wt % Wt % Wt % Wt % Wt % Wt % Biosoft N-300 4.00 4.00 4.00 4.002.00 PolystepA-18S 8.00 Avanel S74 2.00 Tersperse 2735 1.00 TergitolNP-9 2.00 E-14-5 2.00 Amidox C-5 1.00 E-14-2 2.00 CSF 4.00 4.00 4.004.00 Stepanate SXS 8.00 Amphoteric 4.00 TC Dowfax C6L 8.25Tetraethylammonium 12.00 hydroxide CPC 2.00 Tetrasodium 2.00 EDTA Water38.00 39.00 39.00 49.00 43.00 49.00 39.75 51.50 N-Clear 50.00 52.0052.00 43.00 43.00 47.00 36.00 40.50 Total 100.00 100.00 100.00 100.00100.00 100.00 100.00 100.00

TABLE 2A Compositions of the Commercial Surfactants Used In the SodiumSilicate Formulation of the Invention Surfactant Component Type CompanyComposition Biosoft N-300 Anionic Stepan Triethanolamine dodecylbenzenesulfonate PolystepA-18-S Anionic Stepan Sodium (C₁₄₋₁₆) olefin sulfonateAvanel S74 Anionic BASF Alkylpolyether sulfonate, R = C₈, EO = 3Tersperse 2735 Anionic Huntsman Proprietary polycarboxylate TergitolNP-9 Nonionic Dow (UC) Nonylphenolpolyethyoxyethanol EO = 9 E-14-5Nonionic Tomah Poly(5)oxyethylene isodecyloxypropyl amine Amidox C-5Nonionic Stepan Cocoamide 6EO E-14-2 Amphoteric TomahBis(2-hydroxyethyl)isodecyloxypropyl amine Makam CSF Amphoteric McIntyreSodium Cocoamphopropionate Amphoteric TC Amphoteric Tomah Sodiumisohexyloxypropyliminodipropionate* Stepanate SXS Hydrotrope StepanSodium xylene sulfonate Dowfax C6L Hydrotrope Dow Benzene1,1′-oxybis-sec-hexyl deriv., sodium salts CPC Quaternary ZeelandCetylpyridinium chloride Tetraethyl Nucleophile SACHEM, ammonium Inc.hydroxide N-Clear Na Silicate PQ Corp. Sodium silicate, 42 Baume *Thecomposition is believed to be as named. Tomah has not confirmed thiscomposition.

The compositions shown in Table 3 are representative of the acidicpolymer formulation of the invention used for the intended purposes offlocculating or coagulating the emulsified waste. Entry 1 is an acidicpolymer formulation commonly used with silicate formulations containinglower silicate levels. Entry 2 is a common formulation used for microencapsulation of hydrocarbons and chemicals with higher silicateconcentrations. Entry 3 is a common formulation used for microencapsulation of hydrocarbons and chemicals and is a preferredformulation for oxidation of CB Agents with peracetic acid. Thepreparation of the acidic polymer formulation of the invention is asfollows: Calcium chloride is added to the water and stirred intosolution on a magnetic stirrer. Then the surfactant is added followed bythe acid and then the hydrotrope. The polymer solution and aluminumchlorohydrate are added

TABLE 3 Examples of Acidic Polymer Formulations of the Invention Entry1, Entry 2, Entry 3, Component Wt. Percent Wt. Percent Wt. Percent Water71.35 58.72 57.72 Calcium chloride 6.00 6.00 6.00 Cetylpyridiniumchloride 1.00 Phosphoric acid (75%) 1.25 8.00 8.00 Sodium xylenesulfonate 2.00 4.00 4.00 PolyDADMAC 0.40 0.48 0.48 Aluminumchlorohydrate 19.00 22.80 22.80 Total 100.00 100.00 100.00last. The following fluids shown in Table 4 were micro encapsulatedusing the sodium silicate formulation (Table 2 Entry 6) and the acidicpolymer formulation of the invention (Table 3 Entry 2). The fluids weretreated using equal parts silicate and polymer formulations by weight ofthe hydrocarbon fluid, allowed to air dry, TCLP extracted, and analyzedfor leachable TPH. All results are considered to be very low levels ofcontaminant leachability.

TABLE 4 TCLP Results of Micro Encapsulated of Hydrocarbon Fluids EntryLeachable No. Hydrocarbon TPH, ppm 1 Used Motor Oil <1 2 Gasoline <1 3Diesel, No. 2 <1 4 Crude Oil, Bartlesville Sand <1 5 Jet Fuel, JP-8 <1 6Engine Lubricating Oil MIL-PRF-7808 3.84 7 Calibration FluidMIL-PRF-7024 <1 8 Preservative Oil (1010) MIL-PRF-7024 <1 9 AeroshellGrease MIL-G-21164 9.37 10 Hydraulic Fluid MIL-PRF-83282 11.1 11Hydraulic Fluid MIL-PRF-5606, Used 2.65 12 BP Turbo Oil 2389 (SYN)MIL-PRF-7808 1.51

Example 2

A sample of used motor oil (UMO) was micro encapsulated using equalparts silicate (Table 2, Entry 6) and polymer formulations (Table 3,Entry 2) by weight of the used motor oil, allowed to air dry then TCLPextracted and analyzed by gc as shown in Table 5. The BTEX levels werereduced to below the limit of detection for the gc procedure. Most ofthe extractable metals were substantially reduced by the microencapsulation process except for those metals like sodium and calciumpresent in the micro encapsulation formulations. Cadmium and chromiumwere present only at very low levels in the micro encapsulated UMO, butsince the UMO was not acid digested, cadmium and chromium were below thelimit of detection (0.250 ppm). Leachable lead was substantially reducedby micro encapsulation. Even though phosphorus was present in the microencapsulation system, the level of phosphorus from the UMO wassubstantially lowered by micro encapsulation. This experimentdemonstrates the benefit of micro encapsulation to reduce leachableorganic chemicals and metals.

TABLE 5 BETX and Metals Testing in Micro Encapsulated Used Motor Oil.Control, UMO Micro Encapsulated UMO Analyses Result, ppm *Limit, ppmResult, ppm *Limit, ppm BTEX (SW8021B) Benzene 1.73 0.200 ND 0.0500Ethylbenzene 65.8 0.500 ND 0.0500 Toluene 104 0.500 ND 0.0500 Xylenes,Total 376 1.50 ND 0.150 Metals (ICP E200.7) Aluminum <1.25 1.25 3.430.0500 Antimony 0.450 0.250 0.0645 0.0100 Boron 28.2 1.25 0.643 0.100Cadmium <0.250 0.250 0.188 0.00100 Calcium 5.77 1.25 396 5.00 Chromium<0.250 0.250 0.0321 0.0100 Copper 9.92 0.250 0.499 0.0100 Iron 11.5 1.25<0.0500 0.0500 Lead 1.64 0.125 0.326 0.00500 Magnesium 16.5 1.25 6.960.0500 Potassium 17.5 1.25 22.2 0.0500 Sodium <1.25 1.25 2,090 5.00 Tin1.51 1.25 <0.100 0.100 Zinc 33.4 0.250 10.5 0.10 Phosphorus 352 35.83.84 1.00 (M4500-P E) *Limit = Detection Limit

Example 3

A sample of micro encapsulated UMO produced with the inventiveformulations (Table 2 Entry 6 and Table 3 Entry 3) was extractedaccording to the Multiple Extraction Procedure (MEP) EPA Method 1320 toestablish the benefit of micro encapsulation technology for spills. Thisprocedure is designed to simulate the leaching that a waste will undergofrom repetitive precipitation of acid rain on an improperly designedsanitary landfill. The repetitive extractions reveal the highestconcentration of each constituent that is likely to leach in a naturalenvironment. The micro encapsulated samples are first extractedaccording to the Extraction Procedure Toxicity Test Method 1310 andanalyzed for the constituents of concern. Then the solid portions of theextracted waste samples that remain after application of Method 1310 arere-extracted nine times using synthetic acid rain extraction fluid. Ifthe concentration of any constituent of concern increases from the7^(th) or 8^(th) extraction to the 9^(th) extraction, the procedure isrepeated until these concentrations decrease.

In this experiment, the waste was UMO micro encapsulated with a ratio of1/1/1 of the constituents UMO/alkaline sodium silicate/acidic polymerformulations of the invention. The sample was allowed to air dry beforethe initial extraction. The synthetic acid rain extraction fluid is madeby adding an amount of a previously prepared 60/40 weight percentmixture of concentrated sulfuric acid/nitric acids to a large enoughvolume of deionized water to perform all extractions until the pH is3.0+/−0.2.

The extract was analyzed for TPH Diesel (SW8015M), and BTEX (SW8021B).The results are tabulated in Table 6.

TABLE 6 Micro Encapsulated Used Motor Oil, MEP Ethyl TPH Benzene Toluenebenzene Xylenes Extraction Result, Result, Result, Result, Result,Number mg/L mg/L mg/L mg/L mg/L 1 ND 0.0120 0.00900 ND ND 2 ND ND ND NDND 3 ND ND ND ND ND 4 ND ND ND ND ND 5 ND ND ND ND ND 6 ND 0.02100.0170  0.018 0.05 7 ND ND ND ND ND 8 ND ND ND ND ND 9 ND ND ND ND ND10  ND ND ND ND ND Detection Limits: TPH 1 mg/L Benzene 0.00500 mg/LToluene 0.00500 mg/L Ethyl benzene 0.00500 mg/L Xylenes, Total 0.0150mg/L

Example 4

Drill cuttings, 20.00 g, from an on-shore processing facility containingan oil based drilling mud were treated with 1.00 g of the sodiumsilicate solution of the invention (Table 2 Entry 6) and the acidicpolymer formulation of the invention, (Table 2 Entry 2) in a beaker andmixed with a spatula. The mixture was allowed to dry at room temperatureto a light gray color. The micro encapsulate was extracted using the EPATCLP (Method 1311). The analysis (Diesel Range Organics) for TotalPetroleum Hydrocarbons (TPH) was less than 1 ppm (below the detectionlimit).

Example 5 Nucleophilic Hydrolysis of CW Agent Simulants

A strong nucleophile, tetraethylammonium hydroxide, was formulated intothe sodium silicate formulation of the invention shown in Table 2, Entry7. The concentration of the nucleophile was selected using thetitrimetric methods to establish an excess of the molar neutralizationequivalent for the simulant DPCP. The following procedure was used fornucleophilic hydrolysis:

-   -   1. Add a known weight of simulant to an ultrasonic processing        jar and start a timer.    -   2. Add 5.0 ml of the alkaline sodium silicate formulation of the        invention containing the strong nucleophile (Table 2, Entry 7)        to the jar and swirl.    -   3. After five minutes, add 7.0 ml of the acidic polymer        formulation (Table 3 Entry 1) and mix with a spatula for 1        minute at which time the liquid immediately turns into a white        thick paste. Use pH paper to adjust the pH into the pH 6-8 range        with 0.5 ml of either formulation if necessary.    -   4. Add 55 ml of a 50/50 mixture of acetone and methylene        chloride to quench any denaturing reaction.    -   5. Place the jar and its contents on a Pulsar Ultrasonic        processor for 3 minutes to extract any un-reacted simulant and        the reaction by-products from the mixture.    -   6. Filter the mixture over anhydrous sodium sulfate drying agent        into a Turbovap tube.    -   7. Reduce the solvent mixture to one ml in the hot water (55°        C.) Turbovap with a vacuum system.    -   8. Transfer the one ml of liquid mixture to a GC serum capped        vial and add ten micro liters of internal standard by syringe.    -   9. Analyze by gas chromatography (gc) or gc-ms and compare        retention times with internal standards and the known retention        times of the simulants. The gc used was a HP5890 Series II        instrument with a direct inject split/splitless purge & trap        injector, an HP DB-5 megabore column, FID, PID or ECD detection,        with HP Chemstation Enviroquant data analysis software. The gc        analysis was often used to follow the reaction and absolute        conclusive evidence was obtained using gas chromatography        coupled with mass spectroscopy, gc-ms. The particular        instrumentation used was an HP 6890 gc with a splitless        injector, an HP DB-5 megabore column connected to HP 5973 ms        equipped with a turbo pump with HP Chemstation Enviroquant data        analysis software.

When the strong nucleophile was formulated into the sodium silicateformulation, DPCP was detoxified >99.995% (limit of detection, 50 ppm)within 5 minutes and CEPS was detoxified by 97.6% and 98.6% within 5minutes and 15 minutes respectively (Table 7). Most of thedetoxification probably occurred within the first few minutes of theexperiments. As pH is reduced to neutral by the addition of the acidicpolymer formulation, the reaction rate is greatly slowed. DMMP was muchless reactive under these conditions and this time frame resulting inless than 50% detoxification.

TABLE 7 CWA Simulants Micro Encapsulated with a Nucleophilic HydrolysisComponent, Quenched and Extracted From the Microcell Simulant DPCP DMMPCEPS Quench Time G-Agents G-Agents Mustard Five (5) Minutes >99.995%<50% 97.6% Fifteen (15) Minutes >99.995% <50% 98.6%The experiments were repeated on a larger scale in order to gainsensitivity on the gc-ms. The large scale experiment turned into adifficult task in the micro encapsulation process, but sensitivity wasgained to 5 ppm for DPCP corresponding to >99.9995% denaturation. Theseresults (Table 7A) for DPCP and CEPS simulant detoxification fall wellwithin the boundaries of the Sandia Laboratory/Modec Inc. test resultson live agents (Table 7A).

TABLE 7A Results of Modec DF-200HF Foam Agent on Live Agent Testing.Percent Destruction of Chemical Agent Chemical Agent 1 Minute 15 Minutes60 Minutes GD 99.98 99.97 99.98 VX 91.20 99.80 99.88 HD 78.13 98.4699.84

Example 6 Percarbonate Oxidation of CW Agent Simulants

Detoxification of the chemical simulants by oxidation using sodiumpercarbonate (Provox Sodium Percarbonate, OCI Chemical Corp., Decatur,Ala.) was very successful. The sodium silicate solution (Table 2, Entry7) was further modified by adding 5.0 ml of 12 weight percent sodiumpercarbonate to the formulation prior to simulant addition.

-   -   1. Add a known weight of simulant to an ultrasonic processing        jar and start a timer.    -   2. Add 10.0 ml of the alkaline sodium silicate formulation of        the invention (Table 2 Entry 7) containing 5.0 ml of sodium        percarbonate to the jar and swirled.    -   3. After five minutes, add 7.0 ml of the acidic polymer (Table        2, Entry 1) and mix with a spatula for 1 minute at which time        the liquid turns into a white thick paste. Use pH paper to        adjust the pH into the pH 6-8 range with 0.5 ml of either        formulation if necessary.    -   4. Complete steps 4-9 of the procedure in Example 5.

The results are presented in Table 8. After 5 minutes, the DPCP wasdetoxified >99.995% and the G-Agent simulant DMMP was detoxified to91.4%. The CEPS Mustard simulant was detoxified to 95.8% and Malathionto 96.9%. Additionally, Malathion showed a trend from 2, 5 and 10minutes prior to quenching with 94.2%, 96.9% and 97.4% detoxification.

Once again, the important concept is that the reaction rate isunexpectedly rapid (1-2 minutes) and fairly complete after the sodiumsilicate percarbonate oxidation mixture of the invention is added to thesimulant. This is very important when considering the extreme toxicityof the CW Agents. When the pH is neutralized by the addition of theacidic polymer formulation of the invention, the reaction rate is slowedsubstantially as any excess detoxification agent is rendered harmless.

TABLE 8 CW-Agent Simulants Detoxified with Sodium Percarbonate, MicroEncapsulated, Quenched, and Extracted From the Microcell Simulant DPCPDMMP CEPS Malathion Quench Time G-Agent G-Agent Mustard VX-Agent Two (2)Minutes 94.2% Five (5) Minutes >99.995% 91.4% 95.8% 96.9% Ten (10)Minutes 97.4%

Example 7 Peracetic Acid Oxidation of CW Agent Simulants

Detoxification of the CW Agent simulants by using peracetic acidoxidation was equally successful when compared to the percarbonateoxidation. Peracetic acid was added to the acidic polymer formulation(Table 3 Entry 1) prior to simulant addition. The sodium silicateformulation (Table 2 Entry 7) was added to this mix as directed in theprocedure as follows.

-   -   1. Add 4.0 ml of the acidic polymer formulation (Table 3        Entry 1) to a beaker.    -   2. Add 1.5 ml of 35 percent by weight peracetic acid        (Sigma-Aldrich) to the beaker and swirl.    -   3. Start the timer and add known weights of DPCP, CEPS, DMMP, or        Malathion (57% active) simulant to the beaker and swirl for one        minute.    -   4. At the end of one minute, add 6.0 ml of the sodium silicate        formulation Entry 7, Table 2 to the mixture and mix with a        spatula for one minute at which time a solid microencapsulation        mass results. Use pH paper and the 0.5 ml of either formulation        to adjust if necessary the pH to the 6-8 range.    -   5. Complete steps 4-9 of the procedure in Example 4.

After 5 minutes, the G-Agent simulants DPCP and DMMP were detoxifiedto >99.995% and 87.0% respectively. (Table 9). The Mustard simulant CEPSwas detoxified to 98.2% and Malathion to 98.2%. The Malathion experimentwas repeated at 2 and 10 minutes prior to quenching as shown in Table 9with 98.8%, 98.2% and 98.8% detoxification. Thus, the majority ofdetoxification occurred in the first two minutes. The previous trendtoward reaction completion with time for Malathion in Table 9, ifsignificant, was not upheld, but once again it is important to note theextremely rapid reaction rate.

TABLE 9 CW Simulants Micro Encapsulated With Peracetic Acid Oxidation,Quenched and Extraction From the Microcell Simulant Quench Time DPCPDMMP CEPS Malathion Two (2) Minutes 98.8% Five (5) Minutes >99.995%87.0% 98.2% 98.2% Ten (10) Minutes 98.8%

Example 8 Benefit of Micro Encapsulation Process for CB AgentDetoxification

There are several benefits of using a micro encapsulation deliverysystem with an oxidizer versus just applying an oxidizer detoxificationagent alone to CB agents. Certainly, the oxidizer used alone would beexpected to perform equally in the level of detoxification and has beenproven to do so. To observe that the oxidizer mixture with one of themicro encapsulation components performs equally well is a plus. Mostdetoxification agents are not capable of complete detoxification of CWagents; therefore there is a residual presence of the CW agent.Furthermore, a second type of contaminant constitutes some of theby-products of oxidation of the CW agents that may be considered highlyhazardous. These residual agents and by-products can present additionalsafety concerns and would require additional clean-up and disposalprocedures in order to mitigate the hazard. Lastly, a significant issuewith other decontamination products currently approved for use is thatany oxidizer used in their system (i.e. chlorine dioxide, super tropicalbleach, etc.) that is not totally consumed also constitutes a thirdcontaminant type left in place. This residual oxidant represents asafety issue for personnel and a corrosion problem for equipment. Microencapsulation of the residual contamination provides:

-   -   A reduced level of toxicity exposure to all three contaminant        types.    -   Immediate neutralization of any residual oxidation agent to        environmentally safe by-products.    -   A solid form of waste that can be safely and easily recovered        for further treatment or disposal.

Another benefit of the micro encapsulation system is that it provides acompatible delivery system for the detoxification agent. For example,certain surfactants serve to aid in exposing the biological toxant's DNAto the reactive compound. Some of these surfactants are actually knownto have biocidal activity against certain pathogens. A possiblemechanism for spore kill with the acidic polymer formulation system isthe surfactants or solubilizers can act as a softening agent to disruptthe protein coat resulting in breeches whereby the peracetic acid canenter and attack the DNA.

The experiments in Examples 6 and 7 were repeated except the aggressivesolvent extraction in Step 4 (Example 5) was replaced with a standardTCLP extraction procedure (EPA 1311) after air-drying the microencapsulated material at room temperature. The aqueous acidic TCLPextracts were then extracted with methylene chloride/acetone, dried andanalyzed.

All four of the simulants were oxidized with sodium percarbonateincorporated into the silicate formulation (Table 2 Entry 7) followed bymicro encapsulation with the acidic polymer formulation (Table 3Entry 1) in Series 1 of Table 10. Using the same procedure, peraceticacid was incorporated into the acidic polymer formulation (Table 3Entry 1) as the oxidation agent in Series 2 followed by microencapsulation as shown in Table 10. The samples were allowed to air dryand then extracted using the standard TCLP procedure (EPA 1311). TheTCLP extracts were then extracted with methylene chloride/acetone foranalysis of residual simulant. Series 3 is a duplicate of the Series 1experiment performed by an outside laboratory, Green Country Testing inTulsa, Okla., which was in excellent agreement. The results of theoxidations with subsequent micro encapsulation of any residual simulantand the by-products of detoxification were all significantly improvedwhen compared with the data in Tables 8 and 9. The worst case result forDMMP was 99.933% as compared to 87.0% in Table 9 (detection limit 10ppm). The benefit of micro encapsulation is demonstrated by the factthat the level of toxicity was further reduced in most of the results tobelow the level of detection (10 ppm) in Table 10. The residualsimulants were simply not extractable under these conditions. Microencapsulation using the formulations of the invention providesadditional level of protection from the toxicity of any residualCW-Agents. As silica microcapsules dehydrate, the silica shrinks in anirreversible manner, the packing density is increased and the porediameters are diminished, firmly holding the contaminants in place[Ralph K. Iler, The Colloid Chemistry of Silica and Silicates, CornellUniversity Press, Ithaca, N.Y., 1955, p 140-141].

TABLE 10 The Benefit of Micro Encapsulating the Residual By-Products ofChemical Agents. Quench Time = 5 Minutes Simulant Oxidant Series DPCPDMMP CEPS Malathion Series 1. Sodium >99.999% 99.955% 99.985% >99.999%Percarbonate Series 2. Peracetic Acid >99.999% 99.933% >99.999% >99.999%Series 3. Sodium >99.999% 99.935% 99.954% >99.999% Percarbonate

Further tests with dimethylmethylphosphonate (DMMP) were not beconducted as it was established DPCP more closely resembles the G-agentsbecause the Cl⁻ ion is a better leaving group than —OCH₃. Giletto et.al. U.S. Pat. No. 6,569,353 used the same poor leaving group argument inhis observations.

Example 9 CW Agent Detoxification and By-Product Analysis Using gc-ms

The most preferred alkaline silicate and acidic polymer formulations areshown in Table 2 Entry 6 and Table 3 Entry 3 respectively for “Dual-Use”application. Similar experiments using gc-ms analysis show that thesimulants (DPCP, CEPS and 96 percent Malathion) are all oxidized toby-products extending beyond the limits of detection >99.999% (<10 ppm).Even though the results are beyond the limit of detection of 10 ppm forthe gc-ms procedure, the benefits of micro encapsulation are stillanticipated.

In all cases with peracetic acid as the oxidation agent, the optimummicro encapsulation results were obtained within the five-minutes orless, which is of great significance. Any oxidation experiments greaterthan 5 minutes show evidence of oxidation of some of the components ofthe formulations. The procedure for these experiments is as follows:

-   -   1. Add 5.0 ml of the acidic polymer formulation and 0.40 ml of        the 35% peracetic acid to an ultrasonic processing jar. Swirl        until homogeneous.    -   2. Start the timer and immediately add 0.25 g of simulant to the        mixture with swirling for one minute. Set the mixture aside        until five or thirty minutes total time has elapsed.    -   3. At the end of five or thirty minutes, add 7.0 ml of alkaline        sodium silicate formulation to the solution and mix with a        spatula for one minute at which time a solid micro encapsulation        mass results. Use pH paper and the 0.5 ml of either formulation        to adjust the pH to the 6-8 range.    -   4. Repeat Steps 4-9 in Example 5.    -   5. Analyze by gc-ms. The instrumentation used was an HP 6890 gc        with a splitless injector, an HP DB-5 megabore column connected        to HP 5973 ms equipped with a turbo pump with HP Chemstation        Enviroquant data analysis software.

Spectroscopy is used to identify the composition of organic compounds.Normally a combination of mass spectroscopy (ms), nuclear magneticresonance spectroscopy (nmr), infrared spectroscopy (ir) and maybe ultraviolet spectroscopy (uv) are used to absolutely determine the identityof a pure compound. In this effort, gc-ms are used to separate a complexmixture into components. The disappearance of the simulant peak at agiven retention time is used to assess the level of detoxificationsuccess. Interpretation of the individual peaks in the ms is used toassess the identity of the reaction products along with knowledge of theanticipated products that are formed and how well the data matches thems library scan of the pure product. This analysis only holds true tothe extent of the oxidation by-product's solubility in the methylenechloride-acetone extraction solvent used for the gc-ms analysis. Thosecompounds insoluble in methylene chloride of course do not appear in thegc-ms analysis. However, combining the knowledge of the quantitativedisappearance of the original simulant with the identification of themajority of the reaction by-products expected yields information as tothe success of the detoxification process.

Mass Spectroscopic Analysis of G-Agent Simulant DPCP

The simulant DPCP was oxidized with a peracetic acid and the by-productsof the mixture were micro encapsulated after 5 minutes and extractedwith methylene chloride and acetone. Simulant destruction was greaterthan 99.999 percent (limit of detection=10 ppm). Anticipated oxidationproducts of DPCP are: Diphenyl phosphate, (C₆H₅O)₂P(O)OH (molecularweight (Mwt) 250 g/mole), Phenylphosphoric acid, C₆H₅OP(O)(OH)₂ (Mwt 174g/mole) and Phenol, C₆H₅OH (Mwt 94 g/mole). The only by-productidentified in the mass spec was phenol. It appears DPCP was thoroughlyoxidized by the formulations of the invention. Many of the anticipatedby-products of DPCP could be in the form of phosphates or phosphatesalts that are insoluble in the methylene chloride/acetone mixture.

Mass Spectroscopic Analysis of Mustard Simulant CEPS

The simulant CEPS was oxidized with a peracetic acid and the by-productsof the mixture were micro encapsulated after 5 minutes and extractedwith methylene chloride and acetone. Simulant destruction was greaterthan 99.999 percent (limit of detection=10 ppm). Anticipated oxidationproducts of CEPS are: 2-chloroethylphenyl sulfoxide C₆H₅S(O)CH₂CH₂Cl(Mwt 188 g/mole), 2-chloroethylphenyl sulfone C₆H₅S(O)₂CH₂CH₂Cl (Mwt 204g/mole), phenylvinyl sulfone C₆H₅S(O)₂CH═CH₂ (Mwt 168 g/mole), benzenesulfonyl chloride C₆H₅SO₂Cl (Mwt 176 g/mole). 2-Chloroethylphenylsulfone and benzene sulfonyl chloride are among the major by-products ofCEPS oxidation. The sulfoxide products that were not identified wereundoubtedly produced as an intermediate, but upon further oxidationproduced the corresponding sulfones. Phenylvinyl sulfone would morelikely form in an alkaline hydrolysis than an acidic hydrolysisreaction. Unanticipated oxidation products that could possibly beidentified as: 2-Chlorovinylphenyl sulfone C₆H₅S(O)₂CH═CHCl (Mwt 202g/mole), Chloromethylphenyldisulfonoxide C₆H₅S(O)₂S(O)CH₂Cl (Mwt 238g/mole), Diphenyldisulfide C₆H₅SSC₆H₅ (Mwt 218 g/mole), and Benzenesulfonothioic acid, S-phenyl ester C₆H₅S(O)₂SC₆H₅ (Mwt 218 g/mole) weredetected. None of the micro encapsulation components of the inventionwere identified in the CEPS oxidation although one unknown peak alsoidentified in DPCP was present.

Mass Spectroscopic Analysis of VX Simulant Malathion

The simulant Malathion (96%) was used for the VX-Agent was oxidized witha peracetic acid and the by-products of the mixture were microencapsulated after 5 minutes and extracted with methylene chloride andacetone. Simulant destruction was greater than 99.999 percent (limit ofdetection=10 ppm). Anticipated oxidation products of Diethyl succinateC₂H₅CO₂CH₂CH₂CO₂C₂H₅ (Mwt 174 g/mole), Diethylfumarate trans orE-C₂H₅CO₂CH═CHCO₂C₂H₅ (Mwt 172 g/mole), 2-hydroxydiethyl butanediaoate,C₂H₅CO₂CH₂CH(OH)CO₂C₂H₅ (Mwt 190 g/mole), and a malonate sulfonate saltC₂H₅CO₂CH(S(═O)₂O⁻)CH₂CO₂C₂H₅ (Mwt 253) were among the by-products ofMalathion oxidation identified. The presence of the malonate sulfonatesalt is evidence strongly suggesting the cleavage of the P—S bond toform degradation products of lower toxicity than the P—O bond. In thecase of VX-Agent, exclusive cleavage of the P—S bond occurs to yieldnon-toxic ethyl methylphosphonic acid (EMPA), thus preventing formationof highly toxic EA-2192 (S-2-(diisopropylamino)ethylmethyl-phosphonothioc acid), which occurs via exclusive P—O bondcleavage. Maloxon was not present because the peracetic acid oxidationwas too harsh and oxidation went beyond that stage. Maloxon is oftendetected as a by-product of alkaline oxidation.

Example 10 Biological Agent Denaturation and Micro Encapsulation Resultsin Neat Solution

The purpose of this testing was to determine the effectiveness of theinventive compositions without the oxidation agent added just prior touse in the alkaline silicate formulation of the invention, Table 2 Entry8, and a acidic polymer formulation of the invention Table 3, Entry 1.The denaturation reaction was stopped after a period of time by dilutingthe solid micro encapsulation residue with sterile water followed byextraction. Each of these assays were evaluated using establishedmicrobiological methods for obtaining bacterial culture cell counts bythe method of serial dilution.

The method of serial dilutions allows for the extract sample to undergosuccessive dilutions. A small amount of each of the diluted bacteriasamples is then spread onto an agar plate made from sterile broth. Thenumbers of spore colonies that grow on each plate are counted after anincubation period. By working backwards using multiplication with the“dilution factor” a determination of the number of spores in theoriginal sample is made. The initial spore concentrations weredetermined from the colony counts obtained from positive controlscompleted in triplicate. The assayed spore concentration for the controland samples are representative of the spores contained in the suspensionbefore dilution. The survival percentage was determined for each sample.

Hydrolysis Procedure with BW Agent Simulant

A sodium silicate formulation of the invention containingcetylpyridinium chloride, tetrasodium ethylen ediamine tetraacetate, andan amphoteric surfactant, Amphoteric TC (Table 2 Entry 8) was used todetoxify an anthrax simulant. Cetylpyridinium chloride is stable inalkaline systems in the absence of anionic surfactants. The acidicpolymer formulation of the invention used is shown in Table 3 Entry 1.

The spores of organism Bacillus atrophaeus (formerly Bacillus subtilisvar. niger, ATCC 9372) anthrax simulant were suspended in steriledeionized water. The control spore population was determined byestablished procedures to be 4.33×10⁷ spores ml⁻¹. This number was usedfor comparative analysis with each of the samples assayed. The time(Step 4 of the procedure) between addition of the sodium silicateformulation and quenching were 2, 5, 15, and 60 minutes respectively.Then, the samples were diluted with sterile deionized water and platedon brain-heart infusion agar and incubated at 30° C. for 48 hours. Theprocedure for denaturation follows:

-   -   1. Add 1.0 ml of the spore suspension to a beaker and start a        timer.    -   2. Add 5.0 ml of the alkaline sodium silicate formulation of the        invention to the beaker and swirl.    -   3. At a predetermined time interval (1, 4, 14, and 59 minutes),        add 5.0 ml of the acidic polymer formulation and mix with a        spatula for 1 minute at which time the liquid turns into a white        thick paste. Use pH paper and the 0.5 ml of either formulation        to adjust the pH to the 6-8 range.    -   4. Add 10 ml of sterile deionized water to the mixture and        transfer to a 15 ml Flacon tube.    -   5. Place the Falcon tube on a Vortex Genie 2 shaker and        vigorously shake for 30 seconds as a homogeneous distribution of        the paste particles is observed.    -   6. Make serial dilutions (from 1,000 to 10,000,000) of the        initial suspension (control) and the experimental mixtures in        sterile deionized water.    -   7. Transfer aliquots onto brain-heart infusion agar and incubate        at 30° C. for 24 hours.    -   8. Observe the plates, count the colonies and compare with the        controls.

As shown in Table 11, all Entries had a 95% spore kill (1.5-log₁₀reduction). The data in Table

TABLE 11 Spore Kill Efficiency vs. Time on Micro EncapsulationFormulations of the Invention. Log Time Reduction Reduction Entry No.(minutes) in Spores, % in Spores 1 2 94.63 1.5 2 5 95.70 1.6 3 15 95.591.6 4 60 95.13 1.6

11 was very promising and somewhat better than the original test by anout side government official with the formulations of U.S. Pat. No.5,678,238 cited earlier, but the level of denaturation with time did notchange. To be useful in BW-Agent defeat, significant improvements arerequired.

Slight modifications to the sodium silicate formulation of the invention(Table 1, Entry 8) were made to reduce the cetylpyridinium chloride andNa₄EDTA concentrations from 2.00 weight percent to 1.00 weight percenteach and another biocidal agent, trichloromelamine, was incorporated at0.025 weight percent. The acidic polymer formulation is shown in Table2, Entry 1. The procedure above was repeated at 2 and 15 minute exposuretimes. The assayed spore population was 7.08×10⁹ spores 0.8 ml⁻¹. Aslight improvement was observed to 98.79% and 98.82% denaturationrespectively for the two exposure times.

Example 11

The most preferred formulations of the invention for CB Agents, TICs andTMs incorporate the components for the sodium silicate formulation(Table 2 Entry 6) and for the acidic polymer formulation (Table 3 Entry3) for the “dual use” system were evaluated for oxidative detoxificationof BW Agent spore simulants. The acidic polymer formulation was testedat various concentrations of peracetic acid added just prior to sporetreatment in the experiments shown in Table 12 according to theprocedure for bulk detoxification similar to that used in Example 10.

Bulk Detoxification

The spore form of the bacteria B. atrophaeus ATCC 9372 was used as thesurrogate for gram-positive anthrax simulant. It was suspended insterile deionized water. The control spore population of B. atrophaeuswas determined to be 2.743×10⁸/0.1 ml and after dilution 1.09×10⁷ sporesper 0.1 ml. The denaturing effectiveness on B. atrophaeus was determinedafter five minutes exposure to the varying concentrations of peraceticacid/acidic polymer formulation. The concentration of peracetic acid(Aldrich) used was 32 percent by weight and the acidic polymericformulation contained a sporicidal surfactant. The reaction was quenchedwith the sodium silicate formulation to quickly terminate any excessoxidative capacity of the peroxy acid. The micro encapsulated residuewas diluted with sterile water for extraction. The method of serialdilutions allows for the extract sample to undergo successive dilutions.A small amount of each of the diluted bacteria samples is then spreadonto an agar plate made from sterile broth. The number of spore coloniesthat grow on each plate are counted after an incubation period. Byworking backwards using multiplication with the “dilution factor” adetermination of the number of spores in the original sample is made.The initial spore concentrations were determined from the colony countsobtained from positive controls completed in triplicate. The assayedspore concentration for the control and samples are representative ofthe spores contained in the suspension before dilution. The survivalpercentage was determined for each sample.

Entries 1 through 5 in Table 12 were completely denatured (zero sporesremaining) with the peracetic acid/acidic polymer formulation and microencapsulated with the sodium silicate of the invention. But because ofdefinition, the spore kill was a level of log 7 spore reduction definedas 99.99999 percent. The peracetic acid concentration at 0.20 mleffectively denatured 0.5 ml of simulant. Higher concentrations of thealkaline silicate formulation were required to neutralize the excessacid. Since the agar plates had no indication of spore colonies, theywere incubated another 24 hours and checked only to find the absence ofany spores.

TABLE 12 Denaturation and Micro Encapsulation of Bacillus atrophaeusSolution. Entry Number 1 2 3 4 5 Control* Acidic Polymer 5.4 5.2 5.4 5.80 0.0 Formulation, ml 35% Peracetic 0.40 0.20 0.40 0.80 0.40 0.0 acid,ml Bacillus 0.10 0.50 0.50 0.50 0.10 0.10 atrophaeus, ml Sodium Silicate7 7 7 9 0 0.0 Formulation, ml Time, minutes 5 5 5 5 5 Bacillus, % 0 0 00 0 1.09 × 10&/ Remaining 0.1 ml Log Kill 7 7 7 7 7 0 *After appropriatedilution.

Surface Detoxification

In a similar manner the spores of organism B. atrophaeus, ATCC 9372anthrax simulant were suspended in sterile deionized water and used tocontaminate surfaces. A small quantity (0.02 ml) of B. atrophaeus wasspotted on the surfaces of a 1×2 inch samples of glass, wood and carpet.The surface was treated with approximately 5.0 ml of acidic polymerformulation (Table 3 Entry 3) curing agent containing 0.40 ml ofperacetic acid using a pump bottle sprayer capable of delivering a finespray. After 5 minutes, approximately 7.0 ml of alkaline silicateformulation (Table 2 Entry 6) was sprayed on the surface with a secondpump sprayer to quench the oxidant and complete the micro encapsulation.The micro encapsulated denatured B. atrophaeus and any non-denaturedbacillus was washed from the surface using 100 ml of deionized water byimmersing the object in the water, sealing the container and shaking.The sample was plated on brain-heart infusion agar and incubated at 30°C. for 24 hours. The number of viable spores in the original solutionwas 2.10×10⁹ ml⁻¹. The control spore population was determined as4.19×10⁷ spores per 0.02 ml⁻¹. As shown in Table 13, Entry Numbers 1-3had 100% spore kill to a level of log 7 spore reduction. There were nolive spores to count after incubation. As a control, 0.02 ml of B.atrophaeus was spotted on an each of the three surfaces and then washedfrom that surface (without oxidation and micro encapsulation) withdenatured water in a similar fashion to establish the level of recovery,which was very good in all three experiments.

TABLE 13 Denaturation and Micro Encapsulation of B. atrophaeus onSurfaces. Entry Number 1 2 3 Contaminated Material Glass Wood CarpetTERRACAP 4000, ml 5 5 5 35% Peracetic acid, ml 0.40 0.40 0.40 Bacillusatrophaeus, ml 0.02 0.02 0.02 TERRACAP 3000, ml 7 7 7 Time, minutes 5 55 Bacillus, % Remaining 0 0 0 Log Kill 7 7 7 Control Spore Determination5.23 × 10⁷ 3.78 × 10⁷ 2.33 × 10⁷Live Agent Detoxification with the Sterne Strain of B. anthracis.

In December 2006, testing was conducted at the Division HumanEffectiveness Directorate Air Force Research Laboratory in San Antonio,Tex. under the direction of Dr. Johnathan Kiehl to verify the aboveresults in Example 9 against the Sterne strain of B. anthracis. The testresults confirmed the “dual use” micro encapsulation system comprisingthe most preferred formulations of the invention for CB Agents, TICs andTMs incorporate the components for the sodium silicate formulation(Table 2 Entry 6) and for the acidic polymer formulation (Table 3 Entry3) with peracetic acid achieved a log 7 reduction (10⁷ challenge) on allvariations tested in Table 12. The exposure time was 5 minutes for allsamples tested. A formal report was received.

Example 12

Perchloroethylene is a hazardous persistent chemical and falls under thecategory of a TIC. The “dual use” micro encapsulation system of theinvention comprising the most preferred formulations of the inventionfor CB Agents, TICs and TMs incorporate the components for the sodiumsilicate formulation (Table 2 Entry 6) and for the acidic polymerformulation (Table 3 Entry 3) with peracetic acid using peracetic acidwas used to oxidize the toxic perchloroethylene to by-products.Perchloroethylen was oxidized to a residual of 450 ppm (99.861%oxidized) after 30 minutes and 330 ppm residual (99.898% oxidized) after1.5 hours. This implies that the “dual use” micro encapsulation systemof the invention using peracetic acid or another detoxifying agent couldbe used for spills of chlorinated hydrocarbons and other TICs orpossibly even near surface or subsurface remediation of TICcontamination.

These examples demonstrate excellent results obtained using nucleophilichydrolysis, alkaline oxidation and acidic oxidation mechanisms fordetoxification. This demonstrates the novel utility and “distinguishingcharacteristics” of the “dual use” micro encapsulation system fordetoxification of hazardous substances. Nucleophilic hydrolysis alone isnot as versatile as the oxidative approach for G, VX and Mustard Agentsand nucleophilic hydrolysis has the potential for creating highlyhazardous by products with VX. Acidic oxidation with peracetic acid hasdemonstrated excellent results in terms of log kill levels with theanthrax simulant and high levels of detoxification success with CAsimulants with in two to five minutes exposure times.

Although the invention has been illustrated by the preceding examples,it is not to be construed as being limited to the materials employedtherein, rather the invention is directed to the generic area ashereinbefore disclosed. Various modifications and embodiments can bemade without departing from the spirit or scope thereof.

1. A two-part formulation derived from water based solutions having theability to micro encapsulate hydrocarbons and chemicals, comprising: a.a first solution comprising water and a predetermined ratio of a watersoluble alkaline silicate solution having at least one alkali metal anda predetermined ratio of at least one water soluble surfactant, and; b.a second solution comprising water; a predetermined ratio of watersoluble acid; a predetermined ratio of water dispersible polymer; apredetermined ratio of water soluble hydrotrope; a predetermined ratioof at least one water soluble flocculating agent.
 2. The two-partformulation of claim 1, further comprising a predetermined ratio of atleast one water soluble quaternary surfactant agent; and a predeterminedratio of water soluble activating agent.
 3. The two-part formulation ofclaim 1 wherein the first solution contains at least one alkali metalthat is selected from either sodium or potassium.
 4. The two-partformulation of claim 3 wherein said first solution further comprises:between approximately 30 and 55 parts active silicate per hundred partsof solution; a molar ratio of silicon dioxide to said at least onealkali metal in the range from approximately 2:1 to approximately 3.5:1;wherein the pH of said first solution is from approximately 10 to 13;and wherein alkali metal silicate is present in said solution in aconcentration between approximately 20 and 60 percent by weight.
 5. Thetwo-part formulation of claim 1, wherein the first solution containsalkali metal silicate and contains at least one surfactant that isselected from anionic, nonionic, polymeric, or amphoteric typesurfactants, wherein each of said at least one surfactant is present inthe first solution in a concentration between approximately 0.1 to 15percent by weight.
 6. The two-part formulation of claim 1, wherein saidsecond solution further comprises water soluble acid that is selectedfrom the group consisting of mineral or organic acids.
 7. The two-partformulation of claim 6 wherein said water soluble acid is selected froma group consisting of phosphoric acid or acetic acid.
 8. The two-partformulation of claim 7 wherein said water soluble acid is present in thesecond solution in a concentration between approximately 0.1 and 15percent by weight.
 9. The two-part formulation of claim 1, wherein saidsecond solution further contains a water dispersible polymer that isselected from the group consisting of polyamines, polyacrylamides,polyimines and polydially dimethyl ammonium chloride.
 10. The two-partformulation of claim 9 wherein said water dispersible polymer is presentin a concentration between approximately 0.1 and 15 percent by weight.11. The two-part formulation of claim 1, wherein the second solutionalso contains at least one water soluble hydrotrope selected from thegroup consisting of xylene sulfonates, alkyl naphthalene sulfonates,alkylated diphenyl oxide disulfonates, alpha-olefin sulfonates, alkylether sulfates and phosphate esters in a concentration between about 0.5and 10 percent by weight.
 12. The two-part formulation of claim 1,wherein said second solution further comprises at least one watersoluble flocculation agent selected from the group consisting ofaluminium chlorohydrate, calcium chloride, or other metal salts, acids,acid hydrolyzable substances, or silanes present in a concentrationbetween approximately 5 and 65 percent by weight.
 13. The two-partformulation of claim 1, wherein said second solution further comprisesat least one water soluble surfactant.
 14. The two-part formulation ofclaim 13 wherein said at least one water soluble surfactant is acationic surfactant selected from the group consisting of tetrabutylammonium bromide, benzalkonium chloride, benzethonium chloride orcetylpyridinium chloride in a concentration between approximately 0.1and 10 percent by weight.
 15. The two-part formulation of claim 1wherein said second solution further comprises an activating agent. 16.The two-part formulation of claim 15 wherein said activating agent isethylenediaminetetraacetic acid present in the second solution in aconcentration between approximately 0.1 and 10 percent by weight. 17.The two-part formulation of claim 1, wherein said first solution furthercomprises at least one water soluble detoxifying agent, said watersoluble detoxifying agent is selected from the group consisting ofstrong nucleophiles, hydrolyzing agents or oxidants such as tetraethylammonium hydroxide, sodium or potassium hydroxide, sodium percarbonate,sodium perborate, or components to generate oxidants in situ, present oradded to the first solution in a concentration of about 0.1 to 10percent by weight.
 18. The two-part formulation of claim 1, wherein saidsecond solution further comprises at least one water soluble detoxifyingagent, said detoxifying agent is selected from the group consisting ofperacetic acid, other peroxo acids, or components to generate peroxoacids in situ, in a concentration from approximately 0.1 to 10 percentby weight.
 19. A method of using a two-part formulation derived fromwater based solutions having the ability to micro encapsulatehydrocarbon and/or chemical contaminants on surfaces, in soils orsludges, the method comprising: a. preparing a first solution comprisingwater; a predetermined ratio of a water soluble alkaline silicatesolution having at least one alkali metal; and a predetermined ratio ofat least one water soluble surfactant; b. preparing a second solutioncomprising water and: a predetermined ratio of water soluble acid; apredetermined ratio of water dispersible polymer; a predetermined ratioof water soluble hydrotrope; a predetermined ratio of at least one watersoluble flocculating agent; c. allowing said first solution to contactthe hydrocarbon or chemical contaminant by batch mixing, spraying,fogging or misting; d. allowing said second solution to contact thefirst solution and contaminant to form a homogeneous mixture; e.removing said homogeneous mixture.
 20. A method of using a two-partformulation derived from water based solutions having the ability todetoxify and micro encapsulate hazardous chemical and biologicalsubstances such as TIC's, TM's, and CB Agents on surfaces and soils, themethod comprising: a. preparing a first solution comprising water and: apredetermined ratio of at least one water soluble surfactant; and ifthis solution is intended as the detoxifying solution, a predeterminedratio of a water soluble detoxifying agent; b. preparing a secondsolution comprising water and: a predetermined ratio of water solubleacid; a predetermined ratio of water dispersible polymer; apredetermined ratio of water soluble hydrotrope; a predetermined ratioof at least one water soluble flocculating agent; and if this solutionis intended as the detoxifying solution, a predetermined ratio of atleast one water soluble quaternary surfactant agent; c. providing apredetermined ratio of water soluble activating agent; and apredetermined ratio of a water soluble detoxifying agent; d. allowingeither the first solution with an optional detoxifying agent or thesecond solution with the optional detoxifying agent that requires theoptional quaternary surfactant agent and activating agent to contact theTIC's, TMs, and CB agents by batch mixing, spraying, fogging or misting;e. allowing a period of time sufficient for detoxification to occur; f.allowing said second solution to contact the mixture to form a solid wetpaste; g. removing said solid wet paste.